DE102015000814A1 - Biocide equipment of articles with polyoxometalate micro and / or nanoparticles - Google Patents
Biocide equipment of articles with polyoxometalate micro and / or nanoparticles Download PDFInfo
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- DE102015000814A1 DE102015000814A1 DE102015000814.5A DE102015000814A DE102015000814A1 DE 102015000814 A1 DE102015000814 A1 DE 102015000814A1 DE 102015000814 A DE102015000814 A DE 102015000814A DE 102015000814 A1 DE102015000814 A1 DE 102015000814A1
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- CDAISMWEOUEBRE-CDRYSYESSA-N scyllo-inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O CDAISMWEOUEBRE-CDRYSYESSA-N 0.000 description 1
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- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
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- 239000005720 sucrose Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 150000003555 thioacetals Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000012873 virucide Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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- 150000003751 zinc Chemical class 0.000 description 1
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- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
Abstract
Von magnetischen und/oder magnetisierbaren Mikro- und/oder Nanopartikeln freie, biozide Ausrüstungen von Gegenständen, die mindestens einen Typ von funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikel einer mittleren Teilchengröße von 1 bis < 1000 μm enthalten, Verfahren zu ihrer Herstellung und ihre Verwendung.Magnetic and / or magnetizable micro- and / or nanoparticles-free, biocidal equipment of articles comprising at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and or nanoparticles of average particle size from 1 to <1000 microns, process for their preparation and their use.
Description
Gebiet der ErfindungField of the invention
Die vorliegende Erfindung betrifft die biozide Ausrüstung von Gegenständen mit funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikeln.The present invention relates to the biocidal finishing of articles with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles.
Außerdem betrifft die vorliegende Erfindung Gegenstände, die mit funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikeln biozid ausgerüstet sind.In addition, the present invention relates to articles biocidized with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles.
Nicht zuletzt betrifft die vorliegende Erfindung ein Verfahren zur Herstellung von Gegenständen, die mit funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikel biozid ausgerüstet sind.Last but not least, the present invention relates to a process for the preparation of articles biocidized with functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles.
Stand der TechnikState of the art
Der in der vorliegenden Anmeldung zitierte Stand der Technik wird durch Bezugnahme Bestandteil der vorliegenden Anmeldung.The prior art cited in the present application is incorporated by reference into the present application.
Nosokomiale Infektionen oder Krankenhausinfektionen sind Infektionen, die im Zuge eines Aufenthalts oder einer Behandlung in Krankenhäusern oder Pflegeeinrichtungen auftreten. Um diese Krankenhausinfektionen zu verhindern, müssen die Regeln der Hygiene unter anderem auch durch die Körperpflege streng eingehalten werden. Zu diesem Zweck werden den Reinigungs- und Körperpflegemitteln Biozide, wie
- – Akarizide gegen Milben,
- – Algizide gegen Algen,
- – Bakterizide und Bakteriostatika gegen Bakterien und Bakterienfilme,
- – Fungizide gegen Pilze,
- – Insektizide gegen Insekten,
- – mikrobiozide Ausrüstung gegen Keime,
- – Molluskizide gegen Schnecken,
- – Nematizide gegen Fadenwürmer und
- – Viruzide gegen Viren,
- - acaricides against mites,
- - algicides against algae,
- - Bactericides and bacteriostats against bacteria and bacterial films,
- - fungicides against fungi,
- Insecticides against insects,
- - microbiocidal equipment against germs,
- - molluscicides against snails,
- - Nematicides against roundworms and
- - Virucides against viruses,
Beispiele bekannter Biozide sind 10,10'-Oxybisphenoxoarsin (OBPA), Octylisothiazolinon (OIT), Dichlorctylisothiazolinon (DCOIT), Butylbenzisothiazolinon (BBIT), Iodocarb (3-Iod-2-propinylbutylcarbamat), Zink-Pyrithion (Zinksalz von Pyridin-2-thiol-1-oxid), Trichlosan (polychlorierte Phenoxyphenole), Silberionen und Silber, insbesondere in der Form von Silbernanopartikeln.Examples of known biocides are 10,10'-oxybisphenoxoarsine (OBPA), octylisothiazolinone (OIT), dichloroctylisothiazolinone (DCOIT), butylbenzisothiazolinone (BBIT), iodocarb (3-iodo-2-propynyl butylcarbamate), zinc pyrithione (zinc salt of pyridine-2-one). thiol-1-oxide), trichlosan (polychlorinated phenoxyphenols), silver ions and silver, especially in the form of silver nanoparticles.
Mit der weltweit zunehmenden Reistätigkeit von Personen und des zunehmenden Austauschs von Gütern wächst auch die Gefahr der Verbreitung von Krankheiten. Betroffen sind hier insbesondere Orte, an denen eine große Anzahl von Personen zusammenkommt und abgefertigt wird und/oder eine große Anzahl von Gütern umgeschlagen wird, wie Bahnhöfe, Flughäfen und Schiffsterminals. An diesen Orten gibt es zahllose Gegenstände und Oberflächen, die mittelbar oder unmittelbar mit Personen in Kontakt kommen und daher die Gefahr der Übertragung von Krankheitserregern bergen.With the increasing travel of persons around the world and the increasing exchange of goods, the danger of spreading diseases is also growing. In particular, these are places where a large number of people come together and are processed and / or a large number of goods are handled, such as train stations, airports and ship terminals. In these places, there are countless objects and surfaces that come into direct or indirect contact with people and therefore carry the risk of transmission of pathogens.
Weil die bekannten Biozide Nachteile wie ein enges Anwendungsspektrum, eine vergleichsweise hohe Toxizität, die Neigung, Resistenzen und Kreuzresistenzen hervorzurufen, und eine noch weit gehend ungeklärte ökologische Langzeitwirkung aufweisen, können sie nur sehr wenig oder gar nichts zur Lösung dieser global auftretenden Probleme beitragen.Because the known biocides have disadvantages such as a narrow range of applications, a comparatively high toxicity, the tendency to produce resistances and cross-resistance, and a still largely unexplained ecological long-term effect, they can contribute very little or nothing to the solution of these globally occurring problems.
Es stellt sich daher die Aufgabe, biozide Ausrüstungen von Gegenständen bereitzustellen, die die geschilderten Nachteile nicht mehr länger aufweisen, sondern auf Dauer wirksam sind ohne die Umwelt zu belasten.It is therefore an object to provide biocidal equipment of objects that no longer have the disadvantages described, but are effective in the long run without polluting the environment.
Polyoxometallate sind anorganische Polysäuren mit – im Gegensatz zu Isopolysäuren – mindestens zwei verschiedenen Zentralatomen. Heteropolysäuren entstehen aus jeweils schwachen, mehrbasischen Oxosäuren eines Metalls (meist Chrom, Molybdän, Vanadium oder Wolfram) und eines Nichtmetalls (meist Arsen, Iod, Phosphor, Selen, Silicium oder Tellur) als partielle gemischte Anhydride; Beispiel: H3[PM12O40]: 12-Molybdatophosphorsäure (M = Mo) bzw. 12-Wolframatophosphorsäure (M = W). Als zweites Zentralatom können auch Actinoide oder Lanthanoide fungieren; dabei sind die Wolfram-Heteropolysäuren thermisch wesentlich stabiler als die analogen Molybdän-Verbindungen. Als Keggin-Säuren bezeichnet man gelegentlich Heteropolysäuren der allgemeinen Formulierung [(EO4)M12O36]n-8 mit n = Wertigkeit des tetraedrisch koordinierten Elements E (z. B. Bor, Silicium, Zink). Mit oktaedrisch koordiniertem Heteroatom findet man häufig den Heterohexametallat-Typ [(EO6)M6O18]n-12 (Anderson-Evans-Anionen) [vgl. Römpp Online, Version 3.47 »Heteropolysäuren«]. Polyoxometalates are inorganic polyacids with - in contrast to isopolyacids - at least two different central atoms. Heteropoly acids arise from weak, polybasic oxo acids of a metal (usually chromium, molybdenum, vanadium or tungsten) and a non-metal (usually arsenic, iodine, phosphorus, selenium, silicon or tellurium) as partial mixed anhydrides; Example: H 3 [PM 12 O 40 ]: 12-molybdophosphoric acid (M = Mo) or 12-tungstophosphoric acid (M = W). Actinides or lanthanides can also act as the second central atom; The tungsten heteropolyacids are thermally much more stable than the analogous molybdenum compounds. Occasionally, Keggin acids are heteropolyacids of the general formula [(EO 4 ) M 12 O 36 ] n-8 with n = valence of the tetrahedrally coordinated element E (eg boron, silicon, zinc). With octahedral coordinated heteroatom, the heterohexametallate type [(EO 6 ) M 6 O 18 ] n-12 (Anderson-Evans anions) is frequently found [cf. Römpp Online, Version 3.47 "Heteropolyacids"].
In ihrem Artikel
In ihrem Artikel
In ihrem Artikel
In ihrem Artikel
In ihrem Artikel
In ihrem Artikel
In ihrem Artikel
- – [Cu(II)(EnTofloxacin)2(H2O)2]H2[b-Mo8O26].4H2O,
- – [Cu(II)2(Pipemidinsäure)4][d-Mo8O26].4H2O,
- – [Cu(II)2(Norfloxacin)2(H2O)2][b-Mo8O25] und
- – [Cu(II)2(Enoxazin)2(H2O)4][b-Mo8O26].2H2O.
- - [Cu (II) (enotofloxacin) 2 (H 2 O) 2 ] H 2 [b-Mo 8 O 26 ] .4H 2 O,
- - [Cu (II) 2 (pipemidic acid) 4 ] [d-Mo 8 O 26 ] .4H 2 O,
- - [Cu (II) 2 (norfloxacin) 2 (H 2 O) 2 ] [b-Mo 8 O 25 ] and
- - [Cu (II) 2 (enoxazine) 2 (H 2 O) 4 ] [b-Mo 8 O 26 ] .2H 2 O.
In Ihrem Artikel
Aus der amerikanischen Patentanmeldung US 2004/0185078 A1, dem amerikanischen Patent
Aus dem amerikanischen Patent
Aus den amerikanischen Patenten
Aus der amerikanischen Patentanmeldung US 2008/0187601 A1 und den amerikanischen Patenten
Aus der internationalen Patentanmeldung
Das rumänische Patent 122728 offenbart ein Verfahren zum Bleichen von Naturfasern mit Sauerstoff, bei dem POM als Katalysatoren verwendet werden.Romanian Patent 122728 discloses a process for bleaching natural fibers with oxygen using POM as catalysts.
Das moldavische Patent
Aus dem amerikanischen Patent
Aus den amerikanischen Patenten
Aus dem amerikanischen Patent
Aus dem amerikanischen Patent
Dass die Teilchengröße der Polyoxometallate (POM) eine entscheidende Rolle bei der Problemlösung spielen könnte, lässt sich aus dem Stand der Technik nicht ableiten.That the particle size of the polyoxometalates (POM) could play a decisive role in problem solving can not be deduced from the prior art.
In der älteren deutschen Patentanmeldung
Aufgabe der Erfindung Object of the invention
Der vorliegenden Erfindung lag die Aufgabe zu Grunde, neue biozide, insbesondere mikrobiozide, speziell antibakterielle und/oder bakteriostatische Ausrüstungen für Gegenstände vorzuschlagen, die ein breites Anwendungsspektrum und – wenn überhaupt – nur eine sehr geringe Toxizität gegenüber Menschen, Tieren und Pflanzen, Schädlinge ausgenommen, aufweisen. Des Weiteren sollen die bioziden Ausrüstungen keine Resistenzen und Kreuzresistenzen hervorrufen sowie ökologisch unbedenklich und auf Dauer wirksam sein.It is an object of the present invention to propose novel biocidal, especially microbiocidal, especially antibacterial and / or bacteriostatic equipment for articles having a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, excluding pests, exhibit. Furthermore, the biocidal equipment should not cause resistance and cross-resistance, and should be ecologically safe and effective over the long term.
Erfindungsgemäße LösungInventive solution
Demgemäß wurden die von magnetischen und/oder magnetisierbaren Mikro- und/oder Nanopartikeln freien, bioziden Ausrüstungen von Gegenständen gefunden, die mindestens einen Typ von funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikel einer mittleren Teilchengröße von 1 nm bis < 1000 μm enthalten und die im Folgenden als »erfindungsgemäße biozide Ausrüstungen« bezeichnet werden.Accordingly, the biocidal equipments free of magnetic and / or magnetizable micro- and / or nanoparticles have been found of articles comprising at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate Micro- and / or nanoparticles having a mean particle size of 1 nm to <1000 microns and which are referred to below as "biocidal equipment according to the invention".
Außerdem wurde ein Verfahren zur Herstellung der erfindungsgemäßen, von magnetischen und/oder magnetisierbaren Mikro- und/oder Nanopartikeln freien, bioziden Ausrüstungen gefunden, bei dem man mindestens einen Typ von funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikeln einer Teilchengröße von 1 nm bis < 1000 μm auf der Oberfläche der auszurüstenden Gegenstände und/oder in den auszurüstenden Gegenständen fixiert und das im Folgenden als »erfindungsgemäßes Herstellungsverfahren« bezeichnet wird.In addition, a process for the preparation of the invention, of magnetic and / or magnetizable micro- and / or nanoparticles free, biocidal equipment has been found, wherein at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles of a particle size of 1 nm to <1000 microns fixed on the surface of the objects to be equipped and / or in the objects to be equipped and which is hereinafter referred to as "inventive manufacturing process".
Nicht zuletzt wurde die Verwendung von funktionalisierten, nicht funktionalisierten, aggregierten, nicht aggregierten, agglomerierten, nicht agglomerierten, geträgerten und/oder nicht geträgerten Polyoxometallat-Mikro- und/oder -Nanopartikeln einer Teilchengröße von 1 nm bis < 1000 μm für die von magnetischen und/oder magnetisierbaren Nanopartikeln freie, biozide Ausrüstung von Gegenständen gefunden, die im Folgenden als »erfindungsgemäße Verwendung« bezeichnet wird.Last but not least, the use of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported polyoxometalate micro- and / or nanoparticles of particle size from 1 nm to <1000 microns for those of magnetic and / or magnetizable nanoparticles free, biocidal equipment found objects, which is hereinafter referred to as "inventive use".
Vorteile der ErfindungAdvantages of the invention
Im Hinblick auf den Stand der Technik war es überraschend und für den Fachmann nicht vorhersehbar, dass die Aufgabe, die der vorliegenden Erfindung zu Grunde lag mithilfe der erfindungsgemäßen bioziden Ausrüstung von Gegenständen, dem erfindungsgemäßen Herstellungsverfahren und der erfindungsgemäßen Verwendung gelöst werden konnte.In view of the prior art, it was surprising and unforeseeable for the skilled person that the object underlying the present invention could be achieved by means of the biocidal equipment of articles according to the invention, the production method according to the invention and the use according to the invention.
Insbesondere überraschte, dass die erfindungsgemäßen bioziden Ausrüstungen ein breites Anwendungsspektrum und – wenn überhaupt – nur eine sehr geringe Toxizität gegenüber Menschen, Tieren und Pflanzen, Schädlinge ausgenommen, aufwiesen. Des Weiteren riefen die erfindungsgemäßen bioziden Ausrüstungen keine Resistenzen und Kreuzresistenzen hervor und waren ökologisch unbedenklich. Sie waren mithilfe des erfindungsgemäßen Verfahrens in einfacher Weise herstellbar. Sie zersetzten und/oder entmischten sich auch nicht bei längerer Lagerung und/oder ihrem Transport bei wechselnden Temperaturen und wechselnder Luftfeuchtigkeit. Sie konnten in einfacher und sicherer Weise angewendet werden.In particular, it was surprising that the biocidal equipments according to the invention had a broad spectrum of use and, if at all, only a very low toxicity to humans, animals and plants, excluding pests. Furthermore, the biocidal equipment according to the invention did not cause any resistance or cross-resistance and was ecologically safe. They were produced with the aid of the method according to the invention in a simple manner. They do not decompose and / or segregate even during prolonged storage and / or their transport at changing temperatures and changing humidity. They could be applied in a simple and safe way.
Insbesondere überraschte die hohe akarizide Wirkung der erfindungsgemäßen bioziden Ausrüstung insbesondere gegen Milben.In particular, the high acaricidal activity of the biocidal equipment according to the invention surprised in particular against mites.
Des Weiteren konnte die erfindungsgemäßen bioziden Ausrüstungen als
- – Algizide gegen Algen,
- – Bakterizide und Bakteriostatika gegen Bakterien und Bakterienfilme,
- – Fungizide gegen Pilze,
- – Insektizide gegen Insekten,
- – mikrobiozide Ausrüstung gegen Keime,
- – Molluskizide gegen Schnecken,
- – Nematizide gegen Fadenwürmer und
- – Viruzide gegen Viren
- - algicides against algae,
- - Bactericides and bacteriostats against bacteria and bacterial films,
- - fungicides against fungi,
- Insecticides against insects,
- - microbiocidal equipment against germs,
- - molluscicides against snails,
- - Nematicides against roundworms and
- - Viruzide against viruses
Nicht zuletzt ist war ein ganz besonderer Vorteil der erfindungsgemäßen bioziden Ausrüstung, dass sie hervorragend im Rahmen der Prävention und der Therapie von nosokomialen Infektionen oder Krankenhausinfektionen und im Rahmen der Prävention der Übertragung von Infektionen an Gegenständen, die mittelbar oder unmittelbar mit Personen oder Tieren in Kontakt kamen, angewendet werden konnten. Darüber hinaus förderten entsprechend ausgerüstete Verbandmaterialien die Wundheilung und verhinderten die Narbenbildung. Last but not least was a very particular advantage of the biocidal equipment according to the invention, that it excellently in the context of the prevention and therapy of nosocomial infections or hospital infections and in the context of the prevention of the transmission of infections to objects that are directly or indirectly in contact with persons or animals came, could be applied. In addition, appropriately treated dressings promoted wound healing and prevented scarring.
Detaillierte Beschreibung der ErfindungDetailed description of the invention
Die erfindungsgemäße biozide Ausrüstung ist frei von magnetischen und/oder magnetisierbaren Mikro- und/oder Nanopartikeln, wie sie in der älteren deutschen Patentanmeldung
Gibt's mir egal Im Rahmen der vorliegenden Erfindung verweisen die Begriffe »Lösung« und »gelöst« darauf, dass der betreffende Stoff molekulardispers in dem wasserhaltigen Träger verteilt ist.I do not care In the context of the present invention, the terms "solution" and "solved" refer to the fact that the substance in question is molecularly dispersed in the aqueous carrier.
Im Rahmen der vorliegenden Erfindung bezeichnet der Begriff »Nanopartikel« Partikel einer mittleren Teilchengröße von 1 nm bis < 1000 nm.In the context of the present invention, the term "nanoparticles" denotes particles having an average particle size of 1 nm to <1000 nm.
Des Weiteren bezeichnet der Begriff »Mikropartikel« Partikel einer mittleren Teilchengröße von 1 μm bis 1000 μm.Furthermore, the term "microparticles" refers to particles having an average particle size of from 1 .mu.m to 1000 .mu.m.
Im Rahmen der vorliegenden Erfindung werden unter »Gegenständen« mehr oder weniger komplexe Formteile und formneutrale Gegenstände wie Bänder oder Platten verstanden, die sich durch ihre dreidimensionale Gestaltung von formlosen Gegenständen wie Gasen, Flüssigkeiten oder Pulver abheben.In the context of the present invention, "objects" are understood to mean more or less complex shaped parts and shape-neutral objects, such as tapes or plates, which stand out from informal objects such as gases, liquids or powders due to their three-dimensional design.
Der wesentliche Bestandteil der erfindungsgemäßen bioziden Ausrüstungen sind Heteropolysäuren bzw. Polyoxometallate (POM) in der Form von Mikro- und/oder Nanopartikeln einer mittleren Teilchengröße von 1 nm bis < 1000 μm, vorzugsweise 2 nm bis 500 μm, bevorzugt 5 nm bis 250 μm, besonders bevorzugt 5 nm bis 150 μm und insbesondere 5 nm bis 100 μm. Im Folgenden werden sie als »POM-Mikro- und/oder -Nanopartikel« bezeichnet.The essential constituent of the biocidal finishes according to the invention are heteropolyacids or polyoxometalates (POM) in the form of microparticles and / or nanoparticles having an average particle size of 1 nm to <1000 μm, preferably 2 nm to 500 μm, preferably 5 nm to 250 μm, particularly preferably 5 nm to 150 μm and in particular 5 nm to 100 μm. Hereafter, they are referred to as "POM micro and / or nanoparticles."
Die mithilfe der Transmissionselektromikroskopie (TEM), Rasterelektronenmikroskopie (REM), Rastertransmissionselektromikroskopie (RTEM), Rasterkraftmikroskopie (AFM) oder Rastertunnelmikroskopie (TRM) gemessene mittlere Teilchengröße der erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel kann sehr breit variieren und hervorragend den anderen Bestandteilen der erfindungsgemäßen bioziden Ausrüstungen und ihrem jeweiligen Verwendungszweck angepasst werden.The average particle size of the POM micro- and / or nanoparticles to be used according to the invention, which is measured by transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy (RTEM), atomic force microscopy (AFM) or scanning tunneling microscopy (TRM), can vary widely and excellently other components of the biocidal equipment according to the invention and their respective intended use.
Die POM-Mikro- und/oder -Nanopartikel können die unterschiedlichsten Morphologien und geometrischen Formen aufweisen, so dass sie hervorragend den anderen Bestandteilen der erfindungsgemäßen bioziden Ausrüstungen und ihrem jeweiligen Verwendungszweck angepasst werden können.The POM micro- and / or nanoparticles can have a wide variety of morphologies and geometric shapes, so that they can be perfectly adapted to the other components of the biocidal equipment according to the invention and their respective intended use.
So können sie kompakt sein sowie mindestens einen Hohlraum und/oder eine Kern-Schale-Struktur, wobei der Kern und die Schale aus unterschiedlichen Materialien aufgebaut sein können, aufweisen. Sie können auch unterschiedliche geometrische Formen wie Kugeln, Ellipsoide, Würfel, Quader, Pyramiden, Kegel, Zylinder, Rhomben, Dodekaeder, abgestumpfte Dodekaeder, Ikosaeder, abgestumpfte Ikosaeder, Hanteln, Tori, Plättchen oder Nadeln mit kreisförmigem, ovalen, elliptischen, quadratischen, dreieckigen, viereckigen, fünfeckigen, sechseckigen, siebeneckigen, achteckigen oder sternförmigen (drei-, vier-, fünf- oder mehrzackig) Umriss haben. Dabei können gegebenenfalls vorhandene Kanten und Ecken abgerundet sein. Es können sich auch zwei oder mehr Mikro- und/oder Nanopartikel unterschiedlicher Morphologie und/oder geometrischer Form zusammenlagern. Beispielsweise können kugelförmige POM-Mikro- und/oder -Nanopartikel spitze Auswüchse in Kegelform haben. Oder zwei oder drei zylinderförmige POM-Mikro- und/oder -Nanopartikel können sich derart zusammenlagern, dass sie ein T-förmiges oder Y-förmiges Teilchen bilden. Des Weiteren kann ihre Oberfläche Vertiefungen aufweisen, so dass die POM-Mikro- und/oder -Nanopartikel eine erdbeer-, himbeer- oder brombeerförmige Morphologie haben. Nicht zuletzt können die Hanteln, Tori, Nadeln oder Plättchen in mindestens einer Richtung des Raumes gebogen sein.Thus, they can be compact and have at least one cavity and / or a core-shell structure, wherein the core and the shell can be constructed of different materials. They may also have different geometric shapes such as spheres, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, icosahedra, truncated icosahedra, dumbbells, tori, platelets or needles with circular, oval, elliptical, square, triangular , quadrangular, pentagonal, hexagonal, heptagonal, octagonal, or star-shaped (tri-quad, quadrilateral, pentagonal, or polygonal) outline. If necessary, existing edges and corners can be rounded. It is also possible for two or more micro- and / or nanoparticles of different morphology and / or geometric form to be assembled together. For example, spherical POM micro- and / or nanoparticles may have pointed outgrowths in the form of cones. Or, two or three cylindrical POM micro and / or nanoparticles may assemble to form a T-shaped or Y-shaped particle. Furthermore, their surface may have pits so that the POM micro and / or nanoparticles have a strawberry, raspberry or blackberry morphology. Last but not least, the dumbbells, tori, needles or plates can be bent in at least one direction of the room.
Der Durchmesser der POM-Mikro- und/oder -Nanopartikel kann sehr breit variieren und daher hervorragend den anderen Bestandteilen der erfindungsgemäßen bioziden Ausrüstungen und ihrem jeweiligen Verwendungszweck angepasst werden.The diameter of the POM microparticles and / or nanoparticles may vary widely and, therefore, be well adapted to the other components of the biocidal equipment of the invention and to their particular application.
Im Rahmen der vorliegenden Erfindung ist der Durchmesser der erfindungsgemäßen verwendenden POM-Mikro- und/oder -Nanopartikeln, die keine Kugelform aufweisen, gleich der längsten, durch die jeweiligen Mikro- und/oder Nanopartikel gelegten Strecke. In the context of the present invention, the diameter of the POM micro- and / or nanoparticles according to the invention that are not spherically shaped is the same as the longest distance traveled by the respective microparticles and / or nanoparticles.
Vorzugsweise liegt der Durchmesser erfindungsgemäß bevorzugten Nanopartikeln bei 1 nm bis < 1000 μm, vorzugsweise 2 nm bis 500 μm, bevorzugt 5 nm bis 250 μm, besonders bevorzugt 5 nm bis 150 μm und insbesondere 5 nm bis 100 μm.The diameter of preferred nanoparticles according to the invention is preferably 1 nm to <1000 μm, preferably 2 nm to 500 μm, preferably 5 nm to 250 μm, more preferably 5 nm to 150 μm and in particular 5 nm to 100 μm.
Die elementare Zusammensetzung und die Struktur der POM-Mikro- und/oder -Nanopartikel können ebenfalls sehr breit variieren.The elemental composition and structure of the POM micro- and / or nanoparticles may also vary widely.
Bekannt ist beispielsweise die Einteilung der POM in die folgenden Strukturen:
- – das Lindquist-Hexamolybdatanion, Mo6O19 2–,
- – das Decavanadatanion, V10O28 6–,
- – das Paratungstatanion B, H2W12O42 10–,
- – Mo36-Polymolybdate, Mo36O112(H2O)8–,
- – die Strandberg-Struktur, HP2Mo5O23 4–,
- – die Keggin-Struktur, XM12O40 n–,
- – die Dawson-Struktur, X2M18O62 n–,
- – die Anderson-Struktur, XM6O24 n–,
- – die Allman-Waugh-Struktur, X12M18O32 n–,
- – die Weakley-Yamase-Struktur, XM10O36 n–, und
- – die Dexter-Silverton-Struktur, XM12O42 n–.
- The Lindquist hexamolybdate anion, Mo 6 O 19 2- ,
- The decavanadate anion, V 10 O 28 6- ,
- The paratization stat B, H 2 W 12 O 42 10- ,
- Mo36 polymolybddate, Mo 36 O 112 (H 2 O) 8- ,
- - the Strandberg structure, HP 2 Mo 5 O 23 4- ,
- The Keggin structure, XM 12 O 40 n- ,
- The Dawson structure, X 2 M 18 O 62 n- ,
- The Anderson structure, XM 6 O 24 n- ,
- The Allman Waugh structure, X 12 M 18 O 32 n ,
- The Weakley-Yamase structure, XM 10 O 36 n , and
- - the Dexter-Silverton structure, XM 12 O 42 n- .
Die Hochzahl n ist hier eine ganze Zahl von 3 bis 20 bezeichnet die Wertigkeit eines Anions, die in Abhängigkeit von den Variablen X und M variiert.The n-prime number here is an integer from 3 to 20 denoting the valence of an anion that varies depending on the variables X and M.
Als ein weiteres Ordnungsprinzip für POM können die Formeln I bis XIII dienen:
In den Formeln I bis XII steht TM für ein zweiwertiges oder dreiwertiges Übergangsmetallion wie Mn2 +, Fe2 +, Fe3 +, Co2 +, Co3 +, Ni2 +, Cu2+ und Zn2 +. Die Hochzahl t ist eine ganze Zahl und bezeichnet die Wertigkeit eines Anions, die in Abhängigkeit von der Wertigkeit der Variable TM variiert.In the formulas I to XII TM stands for a divalent or trivalent transition metal such as Mn + 2, Fe + 2, Fe + 3, Co + 2, Co + 3, Ni + 2, Cu 2+ and Zn 2+. The superscript t is an integer and denotes the valence of an anion, which varies depending on the significance of the variable TM.
Des Weiteren kommen POM der allgemeinen Formel XIII in Betracht:
In der Formel XIII steht die Variable A für Phosphor, Silicium oder Germanium und der Index x steht für 0 oder für eine ganze Zahl von 1 bis 40. Der Index y steht für eine ganze Zahl von 1 bis 10, der Index a steht für eine ganze Zahl von 1 bis 8 und der Index b ist eine ganze Zahl von 15 bis 150. Die Hochzahl z variiert in Abhängigkeit von der Natur und dem Oxidationsgrad der Variable A. Es kommen auch die Aquakomplexe und die aktiven Fragmente der POM XIII in Betracht. In the formula XIII the variable A stands for phosphorus, silicon or germanium and the index x stands for 0 or for an integer from 1 to 40. The index y stands for an integer from 1 to 10, the index a stands for one integer from 1 to 8 and the index b is an integer from 15 to 150. The z factor varies depending on the nature and the degree of oxidation of the variable A. The aqua complexes and the active fragments of the POM XIII are also suitable.
Wenn der Index x gleich 0 ist, ist y bevorzugt gleich 6-a, wobei der Index a gleich einer ganzen Zahl von 1 bis 5 ist und der Index b gleich 19 ist.When the index x is 0, y is preferably 6-a, where the index a is an integer of 1 to 5 and the index b is 19.
Wenn die Variable A gleich Silicium oder Germanium ist, ist der Index x gleich 2, der Index y gleich 18, der Index a gleich 6 und der Index b gleich 77.When the variable A is silicon or germanium, the index x is 2, the index y is 18, the index a is 6 and the index b is 77.
Wenn die Variable A gleich P ist, ist der Index x gleich 2 oder 4, der Index y gleich 12, 15, 17 oder 30, der Index a gleich 1, 3 oder 6 und der Index b gleich 62 oder 123.When the variable A is P, the index x is 2 or 4, the index y is 12, 15, 17 or 30, the index a is 1, 3 or 6 and the index b is 62 or 123.
Vorzugsweise werden die Anionen I bis XIII in der Form von Salzen mit Kationen, die für die Reinigung und Körperpflege und die pharmazeutische Anwendung zugelassen sind, angewandt.Preferably, the anions I to XIII are applied in the form of salts with cations which are approved for cleansing and personal care and pharmaceutical use.
Beispiele geeigneter Kationen sindExamples of suitable cations are
- – H+, Na+, K+ und NH4 + - H + , Na + , K + and NH 4 +
- – Mono-, Di-, Tri- oder Tetra-(C1-C20-alkylammonium) wie Pentadecyldimethylferrocenylmethylammonium, Undecyldimethylferrocenylmethylammonium, Hexadecyltrimethylammonium, Octadecyltrimethylammonium, Didodecyldimethylammonium, Ditetradecyldimethylammonium, Dihexadecyldimethylammonium, Dioctadecyldimethylammonium, Dioctadecylviologen, Trioctadecylmethylammonium und Tetrabutylammonium,Mono-, di-, tri- or tetra- (C 1 -C 20 -alkylammonium) such as pentadecyldimethylferrocenylmethylammonium, undecyldimethylferrocenylmethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, didodecyldimethylammonium, ditetradecyldimethylammonium, dihexadecyldimethylammonium, dioctadecyldimethylammonium, dioctadecylviologen, trioctadecylmethylammonium and tetrabutylammonium;
- – Mono-, Di-, Tri- oder Tetra-(C1-C20-alkanolammonium) wie Ethanolammonium Diethanolammonium und Triethanolammonium- Mono-, di-, tri- or tetra- (C 1 -C 20 alkanolammonium) such as ethanolammonium diethanolammonium and triethanolammonium
- – Monokationen natürlich vorkommender Aminosäuren wie Histidinium (HISH+), Argininium (ARGH+) oder Lysinium (LYSH+) oder Oligo- oder Polypeptide mit einem oder mehreren protonierten basischen Aminosäurerest(en).Monocations of naturally occurring amino acids such as histidinium (HISH + ), argininium (ARGH + ) or lysinium (LYSH + ) or oligo- or polypeptides having one or more protonated basic amino acid residues.
[Vgl.
Beispiele geeigneter POM gehen aus der Tabelle 1 hervor. Tabelle 1: Summenformeln von geeigneten POMa) a) vgl.
b)
n Zahl, insbesondere ganze Zahl, von 1 bis 50.Examples of suitable POM are shown in Table 1. Table 1: Sum formulas of suitable POMs a) a) cf.
b)
n number, in particular integer, from 1 to 50.
Weitere Beispiele geeigneter POM sind aus dem amerikanischen Patent
Ganz besonders bevorzugt werden H4[Si(W3O10)4].xH2O (CAS-Nr. 12027-43-9) und H3[P(W3O10)4].xH2O (CAS-Nr. 12501-23-4) und oder ihre Salze verwendet.Very particularly preferred are H 4 [Si (W 3 O 10 ) 4 ] .xH 2 O (CAS No. 12027-43-9) and H 3 [P (W 3 O 10 ) 4 ] .xH 2 O (CAS No. 12501-23-4) and or their salts.
Die erfindungsgemäß zu verwendenden POM-Partikel können mithilfe üblicher und bekannter nasschemischer Verfahren hergestellt werden. Es ist aber auch möglich, die POM in Wasser aufzulösen und die resultierende Lösung gegen einen warmen Luftstrom zu sprühen. Außerdem ist es möglich, die Lösung im Vakuum einzustampfen, wobei sie mit IR-Strahlung bestrahlt wird.The POM particles to be used according to the invention can be prepared by means of customary and known wet-chemical processes. However, it is also possible to dissolve the POM in water and to spray the resulting solution against a warm stream of air. In addition, it is possible to evaporate the solution under vacuum, being irradiated with IR radiation.
Die vorstehend beschriebenen POM-Mikro- und/oder -Nanopartikel sind funktionalisiert, nicht funktionalisiert, aggregiert, nicht aggregiert, agglomeriert, nicht agglomerierten, geträgert und/oder nicht geträgert. Beispielsweise können sie funktionalisiert, agglomeriert und geträgert sein. Sie können aber auch nicht funktionalisiert und aggregiert sein.The POM micro- and / or nanoparticles described above are functionalized, non-functionalized, aggregated, unaggregated, agglomerated, non-agglomerated, supported, and / or unsupported. For example, they may be functionalized, agglomerated and supported. But they can also not be functionalized and aggregated.
Die Aggregate sind lockere Anhäufungen von Partikeln, die durch Kohäsion zusammengehalten werden und durch übliche und bekannte Dispergierverfahren nicht verteilt werden können. Ihre innere Oberfläche ist kleiner die Summe der Oberflächen der Primärteilchen.The aggregates are loose aggregates of particles that are held together by cohesion and can not be distributed by conventional and known dispersion methods. Their inner surface is smaller than the sum of the surfaces of the primary particles.
Die Agglomerate sind Zusammenballungen von Primärteilchen und deren Aggregate, die über Kanten und Ecken brückenartig verbunden sind. Ihre innere Oberfläche entspricht in etwa der Summe der Oberflächen der Primärteilchen.The agglomerates are aggregates of primary particles and their aggregates, which are bridged over edges and corners. Their inner surface corresponds approximately to the sum of the surfaces of the primary particles.
Die erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel können „nackt” vorliegen. D. h., dass ihre Oberfläche nicht von einer Hülle umgeben ist und/oder nichtfunktionalisiert ist.The POM micro- and / or nanoparticles to be used according to the invention can be present "naked". That is, their surface is not surrounded by a shell and / or is not functionalized.
Des Weiteren können die erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel von einer Hülle umgeben sein und/oder mindestens eine funktionelle Gruppe tragen. Dabei kann das Material der Hüllen die funktionellen Gruppen tragen oder aber die funktionellen Gruppen können direkt auf der Oberfläche der POM-Mikro- und/oder -Nanopartikel vorliegen.Furthermore, the POM micro- and / or nanoparticles to be used according to the invention may be surrounded by a shell and / or carry at least one functional group. In this case, the material of the shells may carry the functional groups or else the functional groups may be present directly on the surface of the POM micro- and / or nanoparticles.
Das Material der Hülle und/oder die funktionellen Gruppen werden so ausgewählt, dass sich die erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel besonders rasch und homogen in einer organischen und/oder anorganischen Matrix, insbesondere einer organischen und/oder anorganischen polymeren Matrix oder anorganischen keramischen Matrix, die als Trägermaterial und/oder Bindemittel fungiert, verteilen und/oder die physikalischen und/oder chemischen Eigenschaften der POM-Mikro- und/oder -Nanopartikel in einer bestimmten gewünschten Weise modifizieren oder maskieren.The material of the shell and / or the functional groups are selected so that the POM micro- and / or nanoparticles to be used according to the invention are particularly rapidly and homogeneously in an organic and / or inorganic matrix, in particular an organic and / or inorganic polymer Spread matrix and inorganic ceramic matrix, which acts as a carrier material and / or binder, and / or modify or mask the physical and / or chemical properties of the POM micro and / or nanoparticles in a certain desired manner.
Die Hüllen und/oder die funktionellen Gruppen können über kovalente und/oder ionische Bindungen und/oder elektrostatische und/oder Van-der-Waalskräfte an die Oberfläche der POM-Mikro- und/oder -Nanopartikel gebunden sein.The sheaths and / or the functional groups may be attached to the surface of the POM micro- and / or nanoparticles via covalent and / or ionic bonds and / or electrostatic and / or van der Waals forces.
Die Bindung zwischen der Oberfläche der POM-Mikro- und/oder -Nanopartikel und der Hülle und/oder der funktionellen Gruppen kann permanent oder reversibel, d. h. wieder lösbar, sein. The bond between the surface of the POM micro- and / or nanoparticles and the shell and / or the functional groups may be permanent or reversible, ie releasable again.
Die Hüllen können von organischen, anorganischen und metallorganischen, polymeren, oligomeren und niedermolekularen Materialien oder von Kombinationen von mindestens zwei dieser Materialien aufgebaut sein.The shells may be constructed of organic, inorganic and organometallic, polymeric, oligomeric and low molecular weight materials or combinations of at least two of these materials.
Im Folgenden werden Beispiele fürgeeignete funktionelle Gruppen und Materialien für die Hüllen und/oder die Matrices der erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel aufgeführt. Der Fachmann kann die für den jeweiligen Einzelfall besonders gut geeigneten funktionellen Gruppen und Materialien aufgrund der ihm bekannten Eigenschaftsprofile auswählen.The following are examples of suitable functional groups and materials for the shells and / or matrices of the POM micro- and / or nanoparticles to be used in accordance with the invention. The person skilled in the art can select the functional groups and materials which are particularly suitable for the particular case on the basis of the property profiles known to him.
Übliche und bekannte funktionelle Gruppen:Common and known functional groups:
Fluor-, Chlor-, Brom- und Jodatome; Hydroxyl-, Thiol-, Ether-, Thioether-, Amino-, Peroxid-, Aldehyd-, Acetal-, Carboxyl-, Peroxycarboxyl-, Ester-, Amid-, Hydrazid- und Urethangruppen; Imid-, Hydrazon- und Hydroxim-, Amid- und Hydroxamsäuregruppen; Gruppen, die sich von Formamidin, Formamidoxim, Formamidrazon, Formhydrazidin, Formhydrazidoxim, Formamidrazon, Formoxamidin, Formhydroxamoxim und Formoxamidrazon ableiten; Nitril-, Isocyanat-, Thiocyanat-, Isothiocyanat-, Isonitril-, Lactid-, Lacton-, Lactam-, Oxim-, Nitroso-, Nitro-, Azo-, Azoxy-, Hydrazin-, Hydrazon-, Azin-, Carbodiimid-, Azid-, Azan-, Sulfen-, Sulfenamid-, Sulfonamid-, Thioaldehyd-, Thioketon-, Thioacetal-, Thiocarbonsäure-, Sulfonium-, Schwefelhalogenid, Sulfoxid-, Sulfon-, Sulfimin-, Sulfoximin-, Sulton-, Sultam-, Sulfon-, Silan-, Siloxan-, Phosphan-, Phosphinoxid-, Phosphonium-, Phosphorsäure-, Phosphorigsäure-, Phosphonsäure-, Phosphat-, Phosphinat- und Phosphonatgruppen.Fluorine, chlorine, bromine and iodine atoms; Hydroxyl, thiol, ether, thioether, amino, peroxide, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide, hydrazide and urethane groups; Imide, hydrazone and hydroxime, amide and hydroxamic acid groups; Groups derived from formamidine, formamidoxime, formamidrazone, formhydrazidine, formhydrazidoxime, formamidrazone, formoxamidine, formhydroxamoxime and formoxamidrazone; Nitrile, isocyanate, thiocyanate, isothiocyanate, isonitrile, lactide, lactone, lactam, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, azine, carbodiimide , Azide, azane, sulfen, sulfenamide, sulfonamide, thioaldehyde, thioketone, thioacetal, thiocarboxylic acid, sulfonium, sulfur halide, sulfoxide, sulfone, sulfimine, sulfoximine, sultone, sultam, , Sulfonic, silane, siloxane, phosphine, phosphine, phosphonium, phosphoric, phosphorous, phosphonic, phosphate, phosphinate and phosphonate groups.
Übliche und bekannte funktionelle Zusatzstoffe für Kunststoffe:Usual and Known Functional Additives for Plastics:
Beispiele geeigneter Zusatzstoffe sind thermisch und/oder mit aktinischer Strahlung härtbare Reaktiverdünner, niedrig siedende organische Lösemittel und hochsiedende organische Lösemittel („lange Lösemittel”), Wasser, UV-Absorber, Lichtschutzmittel, Radikalfänger, thermolabile radikalische Initiatoren, Photoinitiatoren und -coinitiatoren, Vernetzungsmittel, wie sie in Einkomponentensystemen verwendet werden, Katalysatoren für die thermische Vernetzung, Entlüftungsmittel, Slipadditive, Polymerisationsinhibitoren, Entschäumer, Emulgatoren, Netz- und Dispergiermittel und Tenside, Haftvermittler, Verlaufmittel, filmbildende Hilfsmittel, Sag control agents (SCA), rheologiesteuernde Additive (Verdicker), Flammschutzmittel, Sikkative, Trockungsmittel, Hautverhinderungsmittel, Korrosionsinhibitoren, Wachse, Mattierungsmittel, Verstärkungsfasern oder Vorstufen organisch modifizierter Keramikmaterialien.Examples of suitable additives are thermally and / or actinic-curable reactive diluents, low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water, UV absorbers, light stabilizers, free-radical scavengers, thermolabile free-radical initiators, photoinitiators and co-initiators, crosslinking agents, as used in one-component systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and dispersing agents and surfactants, adhesion promoters, leveling agents, film-forming auxiliaries, sag control agents (SCA), rheology control additives (thickeners), Flame retardants, siccatives, drying agents, anti-skinning agents, corrosion inhibitors, waxes, matting agents, reinforcing fibers or precursors of organically modified ceramic materials.
Beispiele geeigneter thermisch härtbarer Reaktiverdünner sind stellungsisomere Diethyloctandiole oder Hydroxylgruppen enthaltende hyperverzweigte Verbindungen oder Dendrimere, wie sie beispielsweise in den deutschen Patentanmeldungen
Beispiele geeigneter mit aktinischer Strahlung härtbarer Reaktivverdünner sind die in
Beispiele geeigneter niedrigsiedender organischer Lösemittel und hochsiedender organischer Lösemittel („lange Lösemittel”) sind Ketone wie Methylethlyketon, Methylisoamylketon oder Methylisobutylketon, Ester wie Ethylacetat, Butylacetat, Ethylethoxypropionat, Methoxypropylacetat oder Butylglykolacetat Ether wie Dibutylether oder Ethylenglykol-, Diethylenglykol-, Propylenglykol-, Dipropylenglykol-, Butylenglykol- oder Dibutylenglykoldimethyl-, -diethyl- oder -dibutylether, N-Methylpyrrolidon oder Xylole oder Gemische aromatischer und/oder aliphatischer Kohlenwasserstoffe wie Solventnaphtha®, Benzin 135/180, Dipentene oder Solvesso®.Examples of suitable low-boiling organic solvents and high-boiling organic solvents ("long solvents") are ketones such as methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethyl ethoxypropionate, methoxypropyl acetate or butyl glycol acetate ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol , Butylene glycol or Dibutylenglykoldimethyl-, diethyl or -dibutylether, N-methylpyrrolidone or xylenes or mixtures of aromatic and / or aliphatic hydrocarbons such as Solventnaphtha ® , gasoline 135/180, Dipentene or Solvesso ® .
Beispiele geeigneter thermolabiler radikalischer Initiatoren sind organische Peroxide, organische Azoverbindungen oder C-C-spaltende Initiatoren wie Dialkylperoxide, Peroxocarbonsäuren, Peroxodicarbonate, Peroxidester, Hydroperoxide, Ketonperoxide, Azodinitrile oder Benzpinakolsilylether.Examples of suitable thermolabile radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxycarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
Beispiele geeigneter Katalysatoren für die Vernetzung sind Dibutylzinndilaurat, Dibutylzinndioleat, Lithiumdecanoat, Zinkoctoat oder Bismutsalze wie Bismutlactat oder -dimethylolpropionat. Examples of suitable catalysts for the crosslinking are dibutyltin dilaurate, dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts, such as bismuth lactate or dimethylolpropionate.
Beispiele geeigneter Photoinitiatoren und Coinitiatoren werden in
Beispiele geeigneter zusätzlicher Vernetzungsmittel, wie sie in sogenannten Einkomponentensystemen verwendet werden, sind Aminoplastharze, wie sie beispielsweise in
Beispiele für geeignete Entlüftungsmittel sind Diazadicycloundecan oder Benzoin.Examples of suitable deaerating agents are diazadicycloundecane or benzoin.
Beispiele geeigneter Emulgatoren, Netz- und Dispergiermittel oder Tenside sind die üblichen und bekannten anionischen, kationischen, nicht-ionischen und zwitterionische Netzmittel, wie sie beispielsweise in
Ein Beispiel für einen geeigneten Haftvermittler ist Tricyclodecandimethanol.An example of a suitable coupling agent is tricyclodecanedimethanol.
Beispiele für geeignete filmbildende Hilfsmittel sind Cellulose-Derivate wie Celluloseacetobutyrat (CAB).Examples of suitable film-forming auxiliaries are cellulose derivatives such as cellulose acetobutyrate (CAB).
Beispiele geeigneter transparenter Füllstoffe sind solche auf der Basis von Siliziumdioxid, Aluminiumoxid oder Zirkoniumoxid; ergänzend wird noch auf das
Beispiele geeigneter Sag control agents sind Harnstoffe, modifizierte Harnstoffe und/oder Kieselsäuren, wie sie beispielsweise in den Literaturstellen
Beispiele geeigneter rheologiesteuernder Additive sind die aus den Patentschriften
Ein Beispiel für ein geeignetes Mattierungsmittel ist Magnesiumstearat.An example of a suitable matting agent is magnesium stearate.
Beispiele für geeignete Verstärkungsfasern sind Basaltsfasern, Borfasern, Glasfasern, Keramikfasern, Kieselsäurefasern, metallisches Verstärkungsfasern wie Stahlfasern, Aramidfasern, Kevlafasern, Polyesterfasern, Nylonfasern, Teflonfasern, Polyethylenfasern, Polypropylenfasern, PMMA-Fasern, Ligninfasern und Cellulosefasern.Examples of suitable reinforcing fibers are basalt fibers, boron fibers, glass fibers, ceramic fibers, silica fibers, metallic reinforcing fibers such as steel fibers, aramid fibers, Kevlar fibers, polyester fibers, nylon fibers, Teflon fibers, polyethylene fibers, polypropylene fibers, PMMA fibers, lignin fibers and cellulose fibers.
Beispiele geeigneter Vorstufen für organisch modifizierte Keramikmaterialien sind hydrolysierbare metallorganische Verbindungen insbesondere von Silizium und Aluminium.Examples of suitable precursors for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.
Weitere Beispiele für die vorstehend aufgeführten Zusatzstoffe sowie Beispiele geeigneter UV-Absorber, Radikalfänger, Verlaufmittel, Flammschutzmittel, Sikkative, Trocknungsmittel, Hautverhinderungsmittel, Korrosionsinhibitoren und Wachse (B) werden in dem Lehrbuch
Weitere Beispiele für Zusatzstoffe sind Farbstoffe, Buntpigmente, Weißpigmente, fluoreszierende Pigmente und phosphoreszierende Pigmente (Phosphore) sowie die nachfolgend beschriebenen Materialien.Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors) and the materials described below.
Kohlenhydrate:Carbohydrates:
Glycerinaldehyd, Erythrose, Threose, Ribose, Arabinose, Xylose, Lyxose, Fructose, Allose, Altrose, Glucose, Mannose, Idose, Galactose Talose, Rhamnose, Aminozucker wie Neuraminsäure, Muramsäure, Glucosamin, Mannosamin, Aldonsäuren, Ketoaldonsäuren, Aldarsäuren, Pyranosen, Saccharose, Lactose, Raffinose, Panose sowie Homopolysaccharide und Heteropolysaccharide und Proteoglycane, worin der Polysaccharidanteil den Proteinanteil überwiegt, wie Stärke, Dextran, Cyclodextrin, Arabinogalactan, Cellulosen, modifizierte Cellulosen, Lignocellulosen, Chitin, Chitosan, Carageen und Glycosaminoglycane.Glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, fructose, allose, altrose, glucose, mannose, idose, galactose talose, rhamnose, amino sugars such as neuraminic acid, muramic acid, glucosamine, mannosamine, aldonic acids, ketoaldonic acids, aldaric acids, pyranoses, sucrose , Lactose, raffinose, panose and homopolysaccharides and heteropolysaccharides and proteoglycans, wherein the polysaccharide portion outweighs the protein portion, such as starch, dextran, cyclodextrin, arabinogalactan, celluloses, modified celluloses, lignocelluloses, chitin, chitosan, carageen and glycosaminoglycans.
Monoalkohole:Monoalcohols:
Methanol, Ethanol, Propanol, Isopropanol, Butanol, Isobutanol, tert.-Butanol, Amylalkohol Isoamylalkohol, Cyclopentanol, Hexanol, Cyclohexanol, Heptanol, Octanol, Nonanol, Decanol, Undecanol, Dodecanol und ihre Stereoisomeren.Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol isoamyl alcohol, cyclopentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and their stereoisomers.
Polyole:polyols:
Glycerin, Trimethylolpropan, Pentaerythritol, Alditole, Cyclitole, Dimere und Oligomere von Glycerin, Trimethylolpropan, Pentaerythritol, Alditolen and Cyclitolen; vorzugsweise Tetritole, Pentitole, Hexitole, Heptitole und Octitole; bevorzugt Arabinitol, Ribitol, Xylitol, Erythritol, Threitol, Galactitol, Mannitol, Glucitol, Allitol, Altritol, Iditol, Maltitol, Isomaltitol, Lactitol, Tri-, Tetra-, Penta-, Hexa-, Hepta-, Octa-, Nona-, Deca-, Undeca- und Dodecaglycerol, -trimethylolpropan, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, myo-, scyllo-, muco-, chiro-, neo-, allo-, epi- und cis-Inositol.Glycerol, trimethylolpropane, pentaerythritol, alditols, cyclitols, dimers and oligomers of glycerin, trimethylolpropane, pentaerythritol, alditols and cyclitols; preferably tetritols, pentitols, hexitols, heptitols and octitols; preferably arabinitol, ribitol, xylitol, erythritol, threitol, galactitol, mannitol, glucitol, allitol, altritol, iditol, maltitol, isomaltitol, lactitol, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, Deca-, undeca- and dodecaglycerol, -trimethylolpropane, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexanes, 1,2,3,4,5-pentahydroxycyclohexanes, myo-, scyllo-, muco- , chiro-, neo-, allo-, epi- and cis-inositol.
Polyhydroxycarbonsäuren:polyhydroxycarboxylic:
Glycerin-, Citronen-, Wein-Threonin-, Erythron-, Xylon-, Ascorbin-, Glucon-, Galacturon-, Iduron-, Mannuron-, Glucuron-, Guluron-, Glycuron-, Glucar-, Uluson-, Diketogulon- und Lactobionsäure.Glycerol, citron, wine threonine, erythrone, xylon, ascorbic, glucone, galacturon, iduron, mannuron, glucuron, guluron, glycuron, glucar, uluson, diketogulone and lactobionic.
Polyhydroxyphenole und -benzolcarbonsäuren:Polyhydroxyphenols and -benzenecarboxylic acids:
Pyrocatechol, Resorcinol, Hydrochinon, Pyrogallol, 1,2,4-Trishydroxybenzol, Phloroglucin, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-Dihydroxybenzoe- und 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-Trihydroxybenzolsäure (Gallensäure).Pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-trishydroxybenzene, phloroglucinol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-trihydroxybenzoic acid (bile acid).
Amine:amines:
Ammoniak, Ammonium, Mono-, Di- und Trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, -alkylcycloakyl-, -cycloalkylaryl- und -alkylcycloalkylarylamine wie Methylamin, Ethylamin, Propylamin, Isopropylamin, Butylamin, Isobutylamin, tert.-Butylamin, Benzylamin, Cyclohexylamin, Dodecylamin, Kokosamin, Talgamin, Adamantylamin, Anilin, Ethylendiamin, Propylendiamin, Butylendiamin, Piperidin, Piperazin, Pyrazolidin, Pyrazin, Chinuklidin und Morpholin.Ammonia, ammonium, mono-, di- and trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, -alkylcycloakyl-, -cycloalkylaryl- and -alkylcycloalkylarylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert. Butylamine, benzylamine, cyclohexylamine, dodecylamine, cocoamine, tallowamine, adamantylamine, aniline, ethylenediamine, propylenediamine, butylenediamine, piperidine, piperazine, pyrazolidine, pyrazine, quinuclidine and morpholine.
Thiole:thiols:
Mercaptopropionsäure, Dimercaptosuccinsäure (DMSA), Dithiothreitol (DTT) und Octadecanthiol.Mercaptopropionic acid, dimercaptosuccinic acid (DMSA), dithiothreitol (DTT) and octadecanethiol.
Click-Chemie:Click Chemistry:
Verbindungen für Click-Reaktionen wie die kupferkatalysierte Cycloaddition von Aziden und Alkinen, Diels-Alder-Reaktionen, Reaktionen von z. B. Folsäure mit Alkingruppen und dipolare Cycloadditionen mit z. B. Poly(tert.-butylacrylat).Compounds for click reactions such as the copper-catalyzed cycloaddition of azides and alkynes, Diels-Alder reactions, reactions of z. B. folic acid with alkyne groups and dipolar cycloadditions with z. For example, poly (tert-butyl acrylate).
Fettsäuren: fatty acids:
Laurin-, Myristin-, Öl-, Palmitin-, Linol-, Stearin-, Arachin- und Behensäure.Lauric, myristic, oleic, palmitic, linoleic, stearic, arachinic and behenic acid.
Polymere und Oligomere mit funktionellen Gruppen:Polymers and oligomers with functional groups:
Poly(trimethylammoniumethylacrlylat), Polyacrylamid, Poly(D,L-lactid-co-ethylenglykol), Pluronic®, Tetronic®, Polyvinylalkohol (PVA), Polyvinylpyrrolidon (PVP), Poly(alkylcyanoacrylat), Poly(milchsäure), Poly(epsilon-caprolacton), Polyethylenglykol (PEG), Poly(oxyethylen-co-propen)bisphosphonat, Poly(acrylsäure), Poly(methacrylsäure), Hyaluronsäure, Algininsäure, Pektinsäure, Poly(ethylenimin), Poly(vinylpyridin), Polyisobuten, Poly(styrolsulfonsäure), Poly(glycidylmethacrylat), Poly(methacryloyloxyethyltrimethylammoniumchlorid) (MATAC), Poly(L-lysin) und Poly(3-(trimethoxysilyl)propylmethacrylate-r-PEG-methylethermethacrylat), Proteine wie treptavidin, Trypsin, Albumin, Immunoglobulin, Oligo- und Polynucleotide wie DNA und RNA, Peptide wie Arginylglycylasparginsäure (RGD), AGKGTPSLETTP-Peptid (A54), HSYHSHSLLRMF-Peptid (C10) und Gluthathion, Enzyme wie Glucoseoxidase, Dendrimere wie Polypropylenimin-Tetrahexacontaamin-Dendrimer Generation 5 (PPI G5), Poly(amidoamine) (PAMAM) und Guanidin-Dendrimere, Phosphonsäure- und Dithiopyridin-funktionalisierte Polystyrole, funktonalisierte Polyethylenglykole (PEG: Polymerisationsgrad 4-10, insbesondere 5) wie PEG(5)-nitroDOPA, -nitrodopamin, -mimosin, -hydroxydopamin, -hydroxypyridine, -hydroxypyron und -carboxyl.Poly (trimethylammoniumethylacrlylat), polyacrylamide, poly (D, L-lactide-co-ethylene glycol), Pluronic ®, Tetronic ®, Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), poly (alkyl cyanoacrylate), poly (lactic acid), poly (epsilon- caprolactone), polyethylene glycol (PEG), poly (oxyethylene-co-propene) bisphosphonate, poly (acrylic acid), poly (methacrylic acid), hyaluronic acid, alginic acid, pectic acid, poly (ethyleneimine), poly (vinylpyridine), polyisobutene, poly (styrenesulfonic acid) , Poly (glycidyl methacrylate), poly (methacryloyloxyethyltrimethylammonium chloride) (MATAC), poly (L-lysine) and poly (3- (trimethoxysilyl) propylmethacrylate-r-PEG-methylethermethacrylate), proteins such as treptavidin, trypsin, albumin, immunoglobulin, oligo-, and Polynucleotides such as DNA and RNA, peptides such as Arginylglycylasparginsäure (RGD), AGKGTPSLETTP peptide (A54), HSYHSHSLLRMF peptide (C10) and glutathione, enzymes such as glucose oxidase, dendrimers such as polypropyleneimine Tetrahexacontaamin dendrimer generation 5 (PPI G5), poly (amidoamine ) (PA MAM) and guanidine dendrimers, phosphonic acid and dithiopyridine functionalized polystyrenes, functionalized polyethylene glycols (PEG: degree of polymerization 4-10, especially 5) such as PEG (5) -nitroDOPA, -nitrodopamine, -mimosine, -hydroxydopamine, -hydroxypyridine, -hydroxypyrone and carboxyl.
Komplexbildner:complexing agents:
Komplexone wie Nitrilotriessigsäure (NTA) und Ethylendiamintetraessigsäure (EDTA), Phosphonsäuren wie [(2-Aminoethyl)hydroxymethylen]- und [(5-Aminopentyl)hyroxymethylen]diphosphonsäure sowie Kronenether.Complexones such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA), phosphonic acids such as [(2-aminoethyl) hydroxymethylene] - and [(5-aminopentyl) hyroxymethylene] diphosphonic acid and crown ethers.
Metallkomplexe:Metal Complexes:
Übliche und bekannte Koordinations-, Sandwich- und Chelatkomplexe der vorstehend erwähnten Metalle und ihrer Kationen mit organischen und anorganischen Anionen, insbesondere Fluorid, Chlorid, Bromid, Iodid, Ammoniak, Amine, Phosphine, Thiole, Sulfide, Cyanid, Cyanat, Isocyanat, Thiocyanat, Isothiocyanat, Borane, Kohlenmonoxid, Aromaten oder Heteroaromaten.Usual and known coordination, sandwich and chelate complexes of the abovementioned metals and their cations with organic and inorganic anions, in particular fluoride, chloride, bromide, iodide, ammonia, amines, phosphines, thiols, sulfides, cyanide, cyanate, isocyanate, thiocyanate, Isothiocyanate, boranes, carbon monoxide, aromatics or heteroaromatics.
Insbesondere werden Netzmittel oder Tenside als Zusatzstoffe verwendet, da hiermit eine Aggregation und/oder Agglomeration der POM-Mikro- und/oder -Nanopartikel verhindert und eine homogene Verteilung in einer organischen und/oder anorganischen Matrix erzielt wird.In particular, wetting agents or surfactants are used as additives since this prevents aggregation and / or agglomeration of the POM micro- and / or nanoparticles and a homogeneous distribution in an organic and / or inorganic matrix is achieved.
Die vorstehend aufgeführten funktionellen Gruppen und Materialien für die Hüllen der POM-Mikro- und/oder -Nanopartikel sind nur beispielhaft und nicht abschließend aufgezählt. Die Aufzählung soll demnach die Vielfalt der Möglichkeiten verdeutlichen, und der Fachmann kann aufgrund seines allgemeinen Fachwissens ohne Weiteres weitere Möglichkeiten angeben.The above-listed functional groups and materials for the shells of the POM micro- and / or nanoparticles are given by way of example only and not exhaustively. The enumeration is therefore intended to illustrate the variety of possibilities, and the expert can readily specify other possibilities due to his general expertise.
Der Gehalt der erfindungsgemäßen bioziden Ausrüstungen an den erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikeln kann breit variieren und richtet sich insbesondere nach dem jeweiligen Verwendungszweck. Vorzugsweise liegt der Gehalt bei 0,1 bis 100 Gew.-%, bevorzugt 0,5 bis 99,9 Gew.-%, besonders bevorzugt 1 bis 99 Gew.-% und insbesondere 1 bis 90 Gew.-%, jeweils bezogen auf die Gesamtmenge der betreffenden erfindungsgemäßen bioziden Ausrüstung.The content of the biocidal equipment according to the invention in the POM micro- and / or nanoparticles to be used according to the invention can vary widely and depends in particular on the respective intended use. Preferably, the content is 0.1 to 100 wt .-%, preferably 0.5 to 99.9 wt .-%, particularly preferably 1 to 99 wt .-% and in particular 1 to 90 wt .-%, each based on the total amount of biocidal equipment of the present invention.
Ein weiterer bevorzugter Bestandteil der erfindungsgemäßen bioziden Ausrüstungen ist Wasser. Der Wassergehalt der erfindungsgemäßen bioziden Ausrüstungen kann breit variieren und richtet sich ebenfalls im Wesentlichen nach dem jeweiligen Verwendungszweck. Beispielsweise kann das Wasser als Kristallwasser vorhanden sein und/oder an der Oberfläche der erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel adsorbiert sein.Another preferred component of the biocidal equipment of the invention is water. The water content of the biocidal equipment according to the invention can vary widely and also depends essentially on the respective intended use. For example, the water may be present as water of crystallization and / or be adsorbed on the surface of the POM micro- and / or nanoparticles to be used according to the invention.
Die erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel können an andere diamagnetische, nicht magnetisierbare Mikro- und/oder Nanopartikel, vorzugsweise aber Nanopartikel, angelagert oder mit ihnen vermischt sein. Die POM-Mikro- und/oder -Nanopartikel und die diamagnetischen Mikro- und/oder Nanopartikel können durch kovalente und/oder ionische Bindungen, Wasserstoffbrückenbindungen, elektrostatische Anziehung und/oder Van-der-Waalskräfte aneinander gebunden sein.The POM micro- and / or nanoparticles to be used according to the invention can be added to or mixed with other diamagnetic, non-magnetizable micro- and / or nanoparticles, but preferably nanoparticles. The POM micro- and / or nanoparticles and the diamagnetic micro- and / or nanoparticles may be bound together by covalent and / or ionic bonds, hydrogen bonds, electrostatic attraction and / or Van der Waals forces.
Beispiele geeigneter Materialien, aus denen die diamagnetischen Mikro- und/oder Nanopartikel aufgebaut sein können, sind insbesondere
- – Oxide aus der Gruppe, bestehend aus Scandiumoxid, Yttriumoxid, Titandioxid, Zirconiumdioxid, Yttrium-stabilisiertes Zirconiumdioxid, Hafniumdioxid, Vanadiumoxid, Nioboxid, Tantaloxid, Manganoxid, Eisenoxid, Chromoxid, Molybdänoxid, Wolframoxid, Zinkoxid, Oxide der Lanthanide, bevorzugt Lanthanoxid und Ceroxid, insbesondere Ceroxid, Oxide der Actinide, Magnesiumoxid, Calciumoxid, Strontiumoxid, Bariumoxid, Aluminiumoxid, znikdosiertes Aluminiumoxid, Galliumoxid, Indiumoxid, Siliziumdioxid, Germaniumoxid, Zinnoxid, Antimonoxid, Bismutoxid, Zeolithe, Spinelle, Mischoxide aus mindestens zwei der genannten Oxide wie Antimon-Zinn-Oxid, Indium-Zinn-Oxid, Bariumtitanat, Bleititanat oder Bleizirkonattitanat;
- – Phosphate wie Hydroxylapatit oder Calciumphosphat;
- – Sulfide, Selenide und Telluride aus der Gruppe, bestehend aus Arsen-, Antimon-, Wismut-, Cadmium-, Zink-, Eisen-, Silber-, Blei- und Kupfersulfid, Cadmiumselenid, Zinnselenid, Zinkselenid, Cadmiumtellurid und Bleitellurid;
- – Selen und Selendioxid (vgl.
M. Shakibaie et al, »Anti-biofilm activity of biogenic selenium nanoparticles and selenium dioxide against clinical isolates of Staphylococcus aureus, Pseudomonas aeruguinosa, and Proteus mirabilis«, Journal of Trace Elements in Medicine and Biology, Bd. 29, Januar 2015, Seiten 235 bis 241 - – Nitride wie Bornitrid, Siliziumnitrid, Aluminiumnitrid, Galliumnitrid und Titannitrid;
- – Phosphide, Arsenide und Antimonide aus der Gruppe, bestehend aus Aluminiumphosphid Galliumphosphid, Indiumphosphid, Aluminiumarsenid, Galliumarsenid, Indiumarsenid, Aluminiumantimonid, Galliumantimonid, Indiumantimonid;
- – Zintl-Phasen wie Na4Sn9, Na4Pb9, Na2Pb10, Na3[Cu@Sn9], Na7[Ge9CuGe9] oder Na12[Sn2@Cu12Sn20];
- – Kohlenstoff wie Fullerene, Graphen, Graphit, Diamant und funktionalisierte und nicht funktionalisierte Kohlenstoff-Nanoröhrchen;
- – metallorganische Gerüstverbindungen (MOFs);
- – Carbide wie Borcarbid, Siliziumcarbid, Wolframcarbid, Titancarbid oder Cadmiumcarbid;
- – Boride wie Zirkonborid; sowie
- – Silicide wie Molybdänsilicid.
- Oxides from the group consisting of scandium oxide, yttrium oxide, titanium dioxide, zirconium dioxide, yttrium-stabilized zirconium dioxide, hafnium dioxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, iron oxide, chromium oxide, molybdenum oxide, tungsten oxide, zinc oxide, oxides of lanthanides, preferably lanthanum oxide and cerium oxide, in particular cerium oxide, oxides of actinides, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, zinc-doped aluminum oxide, gallium oxide, indium oxide, silicon dioxide, germanium oxide, tin oxide, antimony oxide, bismuth oxide, zeolites, spinels, mixed oxides of at least two of the abovementioned oxides such as antimony-tin oxide. Oxide, indium-tin oxide, barium titanate, lead titanate or lead zirconate titanate;
- - phosphates such as hydroxyapatite or calcium phosphate;
- - sulfides, selenides and tellurides from the group consisting of arsenic, antimony, bismuth, cadmium, zinc, iron, silver, lead and copper sulfide, cadmium selenide, tin selenide, zinc selenide, cadmium telluride and lead telluride;
- - selenium and selenium dioxide (cf.
M. Shakibaie et al, "Anti-biofilm activity of biogenic selenium nanoparticles and selenium dioxide against clinical isolates of Staphylococcus aureus, Pseudomonas aeruginosa, and Proteus mirabilis," Journal of Trace Elements in Medicine and Biology, Vol. 29, January 2015, pp 235 to 241 - Nitrides such as boron nitride, silicon nitride, aluminum nitride, gallium nitride and titanium nitride;
- Phosphides, arsenides and antimonides selected from the group consisting of aluminum phosphide gallium phosphide, indium phosphide, aluminum arsenide, gallium arsenide, indium arsenide, aluminum antimonide, gallium antimonide, indium antimonide;
- Zintl phases such as Na 4 Sn 9 , Na 4 Pb 9 , Na 2 Pb 10 , Na 3 [Cu @ Sn 9 ], Na 7 [Ge 9 CuGe 9 ] or Na 12 [Sn 2 @ Cu 12 Sn 20 ];
- - Carbon such as fullerenes, graphene, graphite, diamond and functionalized and non-functionalized carbon nanotubes;
- - organometallic frameworks (MOFs);
- Carbides, such as boron carbide, silicon carbide, tungsten carbide, titanium carbide or cadmium carbide;
- - borides such as zirconium boride; such as
- Silicides such as molybdenum silicide.
Insbesondere werden Mikro- und/oder Nanopartikel aus physiologisch inerten Materialien verwendet.In particular, micro- and / or nanoparticles of physiologically inert materials are used.
Zu Zwecken der erfindungsgemäßen bioziden Ausrüstung sind die erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel vorzugsweise homogen oder inhomogen in einer organischen und/oder anorganischen Matrix, insbesondere einer organischen und/oder anorganischen polymeren Matrix und/oder in einer anorganischen Keramikmatrix verteilt.For the purposes of the biocidal finish of the invention, the POM micro- and / or nanoparticles to be used according to the invention are preferably distributed homogeneously or inhomogeneously in an organic and / or inorganic matrix, in particular an organic and / or inorganic polymeric matrix and / or in an inorganic ceramic matrix ,
Bei einer inhomogenen Verteilung ist der Gehalt an POM-Mikro- und/oder -Nanopartikel in der Matrix eine Funktion des Abstandes von der Oberfläche der auszurüstenden oder ausgerüsteten Gegenstände. Beispielsweise kann die Konzentration an POM-Mikro- und/oder -Nanopartikeln mit dem Abstand zur Oberfläche kontinuierlich oder diskontinuierlich, stetig oder in Stufen ansteigen oder absinken.In an inhomogeneous distribution, the content of POM micro- and / or nanoparticles in the matrix is a function of the distance from the surface of the articles to be finished or finished. For example, the concentration of POM micro- and / or nanoparticles may increase or decrease continuously or discontinuously with the distance to the surface.
Ein besonderer Vorteil dieser Ausführungsform der erfindungsgemäßen bioziden Ausrüstung ist, dass bei dem mechanischen, physikalischen und/oder chemischen Abtragen des Materials des betreffenden Gegenstands immer wieder eine frische biozide Oberfläche freigelegt wird.A particular advantage of this embodiment of the biocidal equipment according to the invention is that during the mechanical, physical and / or chemical removal of the material of the object in question, a fresh biocidal surface is repeatedly exposed.
Die erfindungsgemäße biozide Ausrüstung kann indes auch als separate Schicht auf der Oberfläche des auszurüstenden Gegenstands vorliegen. Diese Ausführungsform hat den Vorteil der Materialersparnis.However, the biocidal finish of the present invention may also be present as a separate layer on the surface of the article to be finished. This embodiment has the advantage of saving material.
Darüber hinaus können beide Ausführungsformen der erfindungsgemäßen bioziden Ausrüstung miteinander kombiniert werden.In addition, both embodiments of the biocidal equipment according to the invention can be combined.
Die organische polymere Matrix kann aus üblichen und bekannten, thermoplastischen oder duroplastischen Polymeren aufgebaut sein.The organic polymeric matrix may be composed of conventional and known thermoplastic or thermoset polymers.
Als thermoplastische Polymere kommen übliche und bekannte lineare und/oder verzweigte und/oder blockartig, kammartig und/oder statistisch aufgebaute Polyadditionsharze, Polykondensationsharze und/oder (Co)Polymerisate von ethylenisch ungesättigten Monomeren in Betracht.Suitable thermoplastic polymers are customary and known linear and / or branched and / or block-like, comb-like and / or random polyaddition resins, polycondensation resins and / or (co) polymers of ethylenically unsaturated monomers.
Beispiele geeigneter (Co)Polymerisate sind (Meth)Acrylat(co)polymerisate und/oder Polystyrol, Polyvinylester, Polyvinylether, Polyvinylhalogenide, Polyvinylamide, Polyacrylnitrile Polyethylene, Polypropylene, Polybutylene, Polyisoprene und/oder deren Copolymerisate. Examples of suitable (co) polymers are (meth) acrylate (co) polymers and / or polystyrene, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinylamides, polyacrylonitriles, polyethylenes, polypropylenes, polybutylenes, polyisoprenes and / or copolymers thereof.
Beispiele geeigneter Polyadditionsharze oder Polykondensationsharze sind Polyester, Alkyde, Polylactone, Polycarbonate, Polyether, Proteine, Epoxidharz-Amin-Addukte, Polyurethane, Alkydharze Polysiloxane, Phenol-Formaldehyd-Harze, Harnstoff-Formaldehyd-Harze, Melamin-Formaldehyd-Harze, Cellulose, Polysulfide, Polyacetale, Polyethylenoxide, Polycaprolactame, Polylactone, Polylactide, Polyimide, und/oder Polyharnstoffe.Examples of suitable polyaddition resins or polycondensation resins are polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin-amine adducts, polyurethanes, alkyd resins polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides , Polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides, and / or polyureas.
Bekanntermaßen werden die Duroplaste aus mehrfach funktionellen, niedermolekularen und/oder oligomeren Verbindungen durch thermisch und/oder mit aktinischer Strahlung initiierte (Co)Polymerisation hergestellt. Als funktionelle niedermolekulare und/oder oligomere Verbindungen kommen die vorstehend aufgeführten Reaktivverdünner, Katalysatoren und Initiatoren in Betracht.As is known, the thermosets are prepared from polyfunctional, low molecular weight and / or oligomeric compounds by (co) polymerization initiated thermally and / or with actinic radiation. Suitable functional low molecular weight and / or oligomeric compounds are the reactive diluents, catalysts and initiators listed above.
Auch hier ist die vorstehend aufgeführte Aufzählung von Thermoplasten und Duroplasten nicht abschließend, sondern soll insbesondere die Vielfalt der Möglichkeiten verdeutlichen. Weitere geeignete Materialien für die polymere Matrix kann der Fachmann aufgrund seines allgemeinen Fachwissens ohne Weiteres auswählen.Again, the list of thermoplastics and thermosets listed above is not exhaustive, but in particular to illustrate the variety of possibilities. Other suitable materials for the polymeric matrix can be readily selected by those skilled in the art, based on their general knowledge.
Ist die polymere Matrix aus Thermoplasten aufgebaut, werden die POM-Mikro- und/oder -Nanopartikel mithilfe üblicher und bekannter Methoden der Herstellung von Polymerblends in die Thermoplasten eingearbeitet.When the polymeric matrix is built up from thermoplastics, the POM micro- and / or nanoparticles are incorporated into the thermoplastics by conventional and well known methods of making polymer blends.
Ist die polymere Matrix aus Duroplasten aufgebaut, werden die POM-Mikro- und/oder -Nanopartikel in die Ausgangsprodukte der Duroplasten mithilfe üblicher und bekannter Mischmethoden eingearbeitet, wonach die resultierende Mischungen polymerisiert und dadurch vernetzt werden.If the polymeric matrix is composed of thermosets, the POM micro- and / or nanoparticles are incorporated into the starting materials of the thermosets by means of customary and known mixing methods, after which the resulting mixtures are polymerized and crosslinked as a result.
Für die Vermischung der Materialien können die üblichen und bekannten Mischaggregate, wie schnell laufende Rührer, Ultraturrax, Inline-Dissolver, Homogenisierungsdüsen, statische Mischer, Mikrofluidizer, Extruder oder Kneter verwendet werden.For mixing the materials, it is possible to use the customary and known mixing units, such as high-speed stirrers, Ultraturrax, inline dissolvers, homogenizing nozzles, static mixers, microfluidizers, extruders or kneaders.
Die anorganische Keramikmatrix kann aus üblichen und bekannten Gläsern und/oder Keramikmaterialien aufgebaut sein.The inorganic ceramic matrix may be composed of conventional and known glasses and / or ceramic materials.
Die Keramik kann aus einer Oxidkeramik und/oder Nichtoxidkeramik aufgebaut sein. Beispiele geeigneter Keramiken sind Aluminiumoxid-, Borcarbid-, Bornitrid-, Bornitridcarbid-, Calciumsilikat-, Hafniumcarbid-, Siliciumoxid-, Siliciumcarbid-, Siliciumnitrid-, Siliciumoxidnitrid-, Siliciumoxidcarbid-, Siliciumnitridcarbid-, Siliciumoxidnitridcarbid-, Glaskeramik, Tantalcarbid-, Zinkcarbid- oder Zirkonoxidkeramiken, die aus Aluminiumoxid, Borcarbid, Bornitrid, Bornitridcarbid, Calciumsilikat, Hafniumcarbid, Siliciumoxid, Siliciumcarbid, Siliciumnitrid, Siliciumoxidnitrid, Siliciumoxidcarbid, Siliciumnitridcarbid, Siliciumoxidnitridcarbid, Siliciumaluminiumoxidnitrid, Glaskeramik, Tantalcarbid, Zinkcarbid und/oder Zirkonoxid, aufgebaut sind.The ceramic may be constructed of an oxide ceramic and / or non-oxide ceramic. Examples of suitable ceramics are aluminum oxide, boron carbide, boron nitride, boron nitride carbide, calcium silicate, hafnium carbide, silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, silicon oxide carbide, silicon nitride carbide, silicon oxynitride carbide, glass ceramic, tantalum carbide, zinc carbide or zirconia ceramics composed of alumina, boron carbide, boron nitride, boron nitride carbide, calcium silicate, hafnium carbide, silica, silicon carbide, silicon nitride, silicon oxynitride, silicon oxide carbide, silicon nitride carbide, silicon oxynitride carbide, silicon aluminum oxynitride, glass ceramics, tantalum carbide, zinc carbide and / or zirconia.
Im Unterschied zu allen anderen Werkstoffen gilt, dass Keramikerzeugnisse, insbesondere Oxidkeramiken, erst aus den Rohstoffen geformt und dann (also nach der Formgebung) in einem Hochtemperaturprozess oder Sinter-Vorgang mit dem Ziel der Stoffwandlung zur Herstellung stoffschlüssiger Verbindungen zwischen den Rohstoffkörnern in den keramischen Werkstoff überführt werden. Die Rohstoffe haben also – abweichend von den anderen Werkstoffen – zwei grundsätzliche Aufgaben: Sie müssen einerseits die chemische Zusammensetzung der gewünschten keramischen Werkstoffe garantieren und andererseits zuvor deren Formgebung erlauben. Der Keramikrohling weist somit eine deutlich geringere mechanische Festigkeit als beispielsweise ein metallischer Rohling auf. Erträgt deshalb auch die Bezeichnung Grünling, was nichts mit der Farbe zu tun hat.In contrast to all other materials that ceramic products, especially oxide ceramics, first formed from the raw materials and then (ie after molding) in a high-temperature process or sintering process with the goal of material conversion to produce cohesive connections between the raw material grains in the ceramic material be transferred. In contrast to the other materials, the raw materials have two fundamental tasks: on the one hand they must guarantee the chemical composition of the desired ceramic materials and on the other hand they must first allow their shaping. The ceramic blank thus has a significantly lower mechanical strength than, for example, a metallic blank. Therefore bears the name Grünling, which has nothing to do with the color.
Die Herstellung der Keramikerzeugnisse umfasst, unabhängig von der Zusammensetzung, stets folgende Schritte:
- 1. Erzeugung der Rohstoffe,
- 2. Herstellung der keramischen Masse,
- 3. Formgebung,
- 4. Entfernung der Hilfsmittel wie Wasser und/oder organische Additive für die Formgebung,
- 5. Gegebenenfalls mechanische Bearbeitung der Rohlinge oder Glasieren,
- 6. keramischer Brand sowie
- 7. Unterschiedliche Verfahren der Nachbehandlung und Veredelung einschließlich Glasieren oder Dekorieren und nochmaliger Brand.
- 1. production of raw materials,
- 2. Preparation of the ceramic mass,
- 3. shaping,
- 4. Removal of auxiliaries such as water and / or organic additives for shaping,
- 5. Optionally mechanical processing of the blanks or glazing,
- 6. ceramic fire as well
- 7. Different methods of post-treatment and finishing, including glazing or decorating and repeated firing.
Nichtoxidkeramiken enthalten keinen Sauerstoff. Die Anionen sind stattdessen Kohlenstoff, Stickstoff, Bor und Silicium. Eine Ausnahme bilden einige wenige Mischkeramiken, die außer dem genannten Anion auch etwas Sauerstoff enthalten wie z. B. Siliciumaluminiumoxidnitrid.Non-oxide ceramics do not contain oxygen. The anions are instead carbon, nitrogen, boron and silicon. An exception are a few mixed ceramics, which contain some oxygen in addition to the said anion, such as. B. silicon aluminum oxide nitride.
Aber auch die Kationen unterscheiden sich deutlich von den Oxidkeramiken. Wenn Silicium und wo als Kationen auftreten, herrscht die homöopolare Bindung vor, so dass man eigentlich nicht chemisch exakt von Kation und Anion sprechen kann. Befinden sich dagegen zum Beispiel Titan, Zirkonium, Niob oder Wolfram im Kristallgitter dann bilden diese im Werkstoff Schichten mit metallischer Bindung, die mit den in sich homöopolar gebundenen Kohlenstoff-, Stickstoff-, Bor- oder Siliciumschichten heteropolar gebunden sind.But the cations also differ significantly from the oxide ceramics. When silicon and where as cations occur, the homeopolar bond prevails, so that one can not speak chemically exactly of cation and anion. In contrast, if, for example, titanium, zirconium, niobium or tungsten are present in the crystal lattice, then these form layers with metallic bonds in the material which are heteropolar with the homopolar bonded carbon, nitrogen, boron or silicon layers.
Alkali- und Erdalkali-Kationen, die in sehr vielen Oxidkeramiken und nahezu allen Silicatkeramiken enthalten sind, findet man in Nichtoxidkeramiken nicht, es sei denn als Verunreinigung oder – in der Ausnahme – als Dotand.Alkali and alkaline earth cations contained in many oxide ceramics and almost all silicate ceramics are not found in non-oxide ceramics unless as an impurity or, in the exception, as a dopant.
Weitere Einzelheiten zu Nichtoxidkeramiken finden sich in
Glaskeramiken sind polykristalline Festkörper mit mehr als 30% Glasphase die durch gesteuerte Kristallisation von Gläsern hergestellt werden. Die Kristalle entstehen durch Wärmebehandlung eines geeigneten Glases in der Regel farblos und bewirken eine räumliche Streuung des in den Werkstoff eintretenden Lichts.Glass-ceramics are polycrystalline solids with more than 30% glass phase which are produced by controlled crystallization of glasses. The crystals are usually colorless by heat treatment of a suitable glass and cause a spatial dispersion of the light entering the material.
Beispiele geeigneter Glaskeramiken sind das
- – MgOxAl2O3xnSiO2-System (MAS-System),
- – ZnOxAl2O3xnSiO2 (ZAS-System),
- – LiOxAl2O3xnSiO2 (LAS-System) und
- – KMg3[(F, OH)2AlSi3O10] (Phlogopit).
- MgOxAl 2 O 3 xnSiO 2 system (MAS system),
- ZnOxAl 2 O 3 xnSiO 2 (ZAS system),
- - LiOxAl2O 3 xnSiO 2 (LAS system) and
- - KMg 3 [(F, OH) 2 AlSi 3 O 10 ] (phlogopite).
Weitere Einzelheiten zu Glaskeramiken finden sich in
Ganz besonders bevorzugt werden Calciumsilicate verwendet.Most preferably, calcium silicates are used.
Die Calciumsilicate sind übliche und bekannte, am Markt erhältliche Produkte und können durch einen hydrothermalen Verfahrensprozess aus Sinn fein gemahlenen Rohstoffen Kalk und Sand in einer Wassersuspension mit geringem Feststoffanteil und Zusätzen hergestellt werden. Die mineralogische Umwandlungen die Hauptphasen Tobermorit 5CaOx6SiO2x5,5 H2O (etwa 10% Wasser, bis 650°C beständig) und Xonolit 6CaOx6SiO2xH2O (etwa 3% Wasser, bis 850°C beständig) erfolgt in Autoklaven. Die wasserfreie Phase Wollastonit 3CaOx3SiO2 erhöht als Zuschlagstoff die Temperaturbeständigkeit. Die Entwässerungsreaktionen bestimmen den den Grad der Schwindung und somit die Anwendungsgrenzen des Materials.The calcium silicates are common and known products available on the market and can be prepared by a hydrothermal process from sensibly ground raw materials lime and sand in a water suspension with low solids content and additives. The mineralogical transformations the main phases tobermorite 5CaOx6SiO 2 x5.5 H 2 O (about 10% water, resistant to 650 ° C) and xonolite 6CaOx6SiO 2 xH 2 O (about 3% water, resistant to 850 ° C) are carried out in autoclaves. The anhydrous phase wollastonite 3CaOx3SiO 2 increases the temperature resistance as an additive. The dewatering reactions determine the degree of shrinkage and thus the application limits of the material.
Die vorstehend beschriebenen erfindungsgemäßen bioziden Ausrüstungen weisen den weiteren wesentlichen Vorteile auf, dass sie mit zahlreichen anderen Materialien, die sich den Materialien der Matrices unterscheiden, kombiniert werden können. Beispiele geeigneter Materialien dieser Art sind Glas, Holz, Metall, Keramik, Porzellan und/oder Polymere.The biocidal equipments of the present invention described above have the further significant advantages of being compatible with many other materials that are useful in the materials of matrices distinguish, can be combined. Examples of suitable materials of this type are glass, wood, metal, ceramic, porcelain and / or polymers.
Die erfindungsgemäßen bioziden Ausrüstungen und die Gegenstände, die hiermit ausgerüstet sind, können mittels üblicher und bekannter Formungsverfahren hergestellt werden. Vorzugsweise werden sie mithilfe des erfindungsgemäßen Herstellungsverfahrens, bei dem mindestens ein Typ der vorstehend beschriebenen erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikein auf und/oder in den biozid auszurüstenden Gegenständen fixiert werden.The biocidal equipment of the invention and the articles which are hereby equipped can be produced by means of customary and known shaping methods. Preferably, they are fixed by means of the production process according to the invention, in which at least one type of the above-described POM micro- and / or nanoparticles to be used according to the invention are fixed on and / or in the biocidal articles.
Vorzugsweise wird dies mithilfe additiver, d. h. anhäufender, aufbauender Fabrikatoren, insbesondere digital gesteuerter, additiver Fabrikatoren, bewerkstelligt.Preferably, this is done using additive, i. H. accumulating, building factory, especially digitally controlled, additive manufacturers, accomplished.
Vorzugsweise werden als digital gesteuerte, additive Fabrikatoren 3D-Drucker verwendet, wobei die Geometrie der Gegenstände durch CAD/CAM-Programme vorgegeben wird.Preferably, 3D printers are used as digitally controlled additive manufacturers, the geometry of the objects being predetermined by CAD / CAM programs.
Vorzugsweise werden 3D-Drucker verwendet, die für das selektives Laserschmelzen, das selektive Elektronenstrahlschmelzen, das selektive Lasersintern, die Stereolithografie, das Digital Light Processing, das Polyjet-Modeling, das Kaltgasspritzen oder das Schmelzschichten ausgelegt sind.Preferably, 3D printers designed for selective laser melting, selective electron beam melting, selective laser sintering, stereolithography, digital light processing, polyjet modeling, cold gas spraying or melt layers are used.
Die Auswahl der Aufbautechnik richtet sich insbesondere nach den physikalisch-chemischen Eigenschaften der erfindungsgemäß zu verwendenden POM-Mikro- und/oder -Nanopartikel und Matrixmaterialien oder ihrer Vorstufen.The choice of the construction technique depends in particular on the physico-chemical properties of the POM micro- and / or nanoparticles and matrix materials or their precursors to be used according to the invention.
So werden in einer ersten bevorzugten Variante des erfindungsgemäßen Herstellungsverfahrens die Ausgangsprodukte separat oder als Gemisch mindestens zweier Ausgangsprodukte als formlose Fluide mindestens einem additiven, insbesondere digital gesteuerten, additiven, Fabrikator zudosiert und mithilfe des mindestens einen additiven, insbesondere digital gesteuerten, additiven, Fabrikators unter gleichzeitiger Verfestigung der Ausgangsprodukte zu den mit den erfindungsgemäßen bioziden Ausrüstungen versehenen Gegenständen insbesondere digital gesteuert schichtweise angehäuft, bis mindestens ein vorgegebenes, insbesondere digital vorgegebenes, Formteil aufgebaut ist. Diese Variante des erfindungsgemäßen Verfahrens eignet sich besonders gut für die Herstellung komplexer, Formteile auf der Basis von Duroplasten.Thus, in a first preferred variant of the production process according to the invention, the starting materials are metered separately or as a mixture of at least two starting materials as formless fluids at least one additive, in particular digitally controlled, additive, factory and with the aid of at least one additive, in particular digitally controlled, additive, factory under simultaneous Solidification of the starting materials to the objects provided with the biocidal equipment according to the invention in particular accumulated in layers, accumulated in layers until at least one predetermined, in particular digitally predetermined, molded part is constructed. This variant of the method according to the invention is particularly suitable for the production of complex, molded parts based on thermosets.
In einer zweiten bevorzugten Variante werden die Ausgangsprodukte miteinander vermischt, so dass mindestens ein fester, formneutraler, mit einer erfindungsgemäßen bioziden Ausrüstung versehener Gegenstand resultiert. Danach wird der Gegenstand in einen formlosen, fluiden Zustand überführt und in diesem Zustand mindestens einem additiven, insbesondere digital gesteuerten additiven, Fabrikator zudosiert und mithilfe des mindestens einen additiven, insbesondere digital gesteuerten, additiven, Fabrikators unter gleichzeitiger Verfestigung des Fluids insbesondere digital gesteuert schichtweise angehäuft wird, bis mindestens ein vorgegebenes, insbesondere digital vorgegebenes, Formteil aufgebaut ist.In a second preferred variant, the starting materials are mixed together, so that at least one solid, shape-neutral, provided with a biocidal finish according to the invention article results. Thereafter, the object is converted into an informal, fluid state and added in this state at least one additive, in particular digitally controlled additive, factory and using the at least one additive, in particular digitally controlled, additive, factory with simultaneous solidification of the fluid in particular digitally piled in layers piled is until at least a predetermined, in particular digitally predetermined, molded part is constructed.
In einer dritten bevorzugten Variante des erfindungsgemäßen Herstellungsverfahrens werden die Ausgangsprodukte miteinander vermischt, so dass mindestens ein festes, formloses, mit der erfindungsgemäßen bioziden Ausrüstung versehenes Pulver resultiert. Anschließend wird das mindestens eine Pulver einem additiven, insbesondere digital gesteuerten additiven, Fabrikator zudosiert und mithilfe des mindestens einen additiven, insbesondere digital gesteuerten additiven, Fabrikators digital gesteuert angehäuft, bis mindestens ein vorgegebenes, insbesondere digital vorgegebenes, Formteil resultiert.In a third preferred variant of the production process according to the invention, the starting materials are mixed together so that at least one solid, formless powder provided with the biocidal finish according to the invention results. Subsequently, the at least one powder is added to an additive, in particular digitally controlled additive, factory and added digitally piled using the at least one additive, in particular digitally controlled additive, factory, until at least one predetermined, in particular digitally predetermined, molded part results.
Bei dem erfindungsgemäßen Herstellungsverfahren besteht aber auch die Möglichkeit, dass ein biozid ausgerüstetes Formteil derart aufgebaut wird, dass es alternierend Bereiche mit hoher Konzentration an POM-Mikro- und/oder -Nanopartikeln und Bereiche mit niedriger Konzentration und/oder Bereiche ohne POM-Mikro- und/oder -Nanopartikel aufweist. Dies kann dadurch erzielt werden, dass die Zufuhr der POM-Mikro- und/oder -Nanopartikel enthaltenden Ausgangsprodukte unterbrochen wird und stattdessen eine Schicht aus einem thermoplastischen Polymeren oder die Ausgangsprodukte für einen Bereich, der keine POM-Mikro- und/oder -Nanopartikel oder eine andere Konzentration an POM-Mikro- und/oder -Nanopartikeln aufweist, aufgetragen werden, wonach erneut eine Schicht der ersten POM-Mikro- und/oder -Nanopartikel enthaltenden Ausgangsprodukte aufgetragen wird. Dieser Vorgang kann mehrfach wiederholt werden.However, in the production method according to the invention, it is also possible for a biocidal molding to be constructed in such a way that it alternately contains regions with a high concentration of POM micro- and / or nanoparticles and regions with low concentration and / or regions without POM micropores. and / or nanoparticles. This can be achieved by interrupting the supply of the starting materials containing POM micro- and / or nanoparticles and instead a layer of a thermoplastic polymer or the starting materials for a region containing no POM micro- and / or nanoparticles or a different concentration of POM micro- and / or nanoparticles are applied, after which again a layer of the first POM micro- and / or nanoparticles-containing starting materials is applied. This process can be repeated several times.
Im Rahmen der vorliegenden Erfindung bedeutet „formlos”, dass das betreffende Material keine festgelegte Form hat, sondern sich den Formen eines Behältnisses anpasst. Formlose Materialien sind daher flüssig oder gasförmig.In the context of the present invention, "informal" means that the material in question has no fixed shape but adapts to the shapes of a container. Formless materials are therefore liquid or gaseous.
Die vorstehend genannten Verfahren können auch durch so genannte Aufklapp-Herstelltechniken ergänzt werden, bei denen zunächst zweidimensionale Strukturen auf einem gestreckten, elastischen Material hergestellt werden, die beim Entspannen von selbst in die gewünschte dreidimensionale Struktur aufklappen (vgl.
Im Rahmen der vorliegenden Erfindung bedeutet „formneutral”, dass das betreffende Material platten-, band- oder drahtförmig ist.In the context of the present invention, "shape-neutral" means that the material in question is plate-shaped, ribbon-shaped or wire-shaped.
Die erfindungsgemäße biozide Ausrüstung eignet sich für alle Gegenstände, die mittelbar oder unmittelbar mit Menschen oder Tieren in Kontakt kommen. Dies bedeutet, dass Anwendungsmöglichkeiten praktisch unbegrenzt sind. Um nur einige Beispiele zu nennen, lassen sich
- – Prothesen,
- – Kopfhörer,
- – Hörgeräte,
- – Ohrstöpsel,
- – Brillen,
- – Sexspielzeuge,
- – Toiletten,
- – Schalter,
- – Handys,
- – Telefonhörer,
- – Keyboards,
- – Musikinstrumente jeder Art,
- – Wände,
- – Holz,
- – Möbel jeglicher Art,
- – Fliesen,
- – Fußböden,
- – Türen und Türgriffe,
- – Badutensilien wie Duschköpfe und Wasserhähne,
- – medizinische und nicht medizinische Implantate,
- – Glasrahmen,
- – Schuhe und Schuheinlagen,
- – Schutzkleidung,
- – Laboratorien, insbesondere biologische und mikrobiologische Laboratorien,
- – Zellkulturen,
- – Nährmedien
- – Krankenhäuser, insbesondere Operationssäle,
- – Imprägnierungen, die durch Aufsprühen eines POM-Mikro- und/oder -Nanopartikel enthaltenden Aerosols aufgetragen werden,
- – Griffe an Einkaufswagen,
- – Bestecke,
- – Geschirr,
- – sterile Folien und Behälter aus Glas, Metall oder Kunststoff, insbesondere für Zellkulturen, Getränke und Lebensmittel,
- – Unterwasser-Antifouling-Ausrüstung,
- – Fahrradgriffe und Motorradgriffe,
- – das Innere von Transportmitteln wie Boote, Schiffe, Züge, Automobile, Lastwagen oder Flugzeuge,
- – Klimaanlagen,
- – Heizungen, insbesondere Öfen und Blockheizungen,
- – Lüftungssysteme,
- – befeuchtende oder enfeuchtende Raumbelüfter,
- – kaschierte Folien, insbesondere aus Kunststoff,
- – Glasuren für Keramiken
- – Füllstoffe, insbesondere Füllstoffe für Kissen, Polster oder Matratzen und
- – Tone, Lehme und Böden
- - prostheses,
- - Headphone,
- - hearing aids,
- - Ear plug,
- - glasses,
- - sex toys,
- - toilets,
- - Switch,
- - cell phones,
- - telephone receiver,
- - Keyboards,
- - musical instruments of all kinds,
- - Walls,
- - Wood,
- - furniture of any kind,
- - tiles,
- - floors,
- - doors and door handles,
- - bathroom utensils such as shower heads and faucets,
- - medical and non-medical implants,
- - glass frame,
- - shoes and shoe inserts,
- - protective clothing,
- - laboratories, in particular biological and microbiological laboratories,
- - cell cultures,
- - Culture media
- - hospitals, in particular operating theaters,
- Impregnations applied by spraying on a aerosol containing POM micro- and / or nanoparticles,
- - handles on shopping trolleys,
- - cutlery,
- - Dishes,
- Sterile films and containers made of glass, metal or plastic, in particular for cell cultures, drinks and food,
- - underwater anti-fouling equipment,
- - bicycle grips and motorcycle grips,
- - the interior of means of transport such as boats, ships, trains, automobiles, trucks or aircraft,
- - air conditioners,
- - heaters, in particular ovens and block heaters,
- - ventilation systems,
- - humidifying or moisturizing room aerators,
- Laminated films, in particular of plastic,
- - Glazes for ceramics
- Fillers, in particular fillers for pillows, upholstery or mattresses and
- - Clays, loams and floors
Aufgrund der vorliegenden technischen Lehre kann der Fachmann ohne Weiteres, d. h. ohne eigene erfinderische Tätigkeit, zahlreiche weitere Anwendungsmöglichkeiten angeben. On the basis of the present technical teaching, a person skilled in the art can readily specify numerous other possible applications, ie without his own inventive step.
Es versteht sich, dass die vorstehend genannten und nachstehend näher erläuterten Merkmale nicht nur in den angegebenen Kombinationen und Konfigurationen, sondern auch in anderen Kombinationen und Konfigurationen oder in Alleinstellung einsetzbar sind, ohne den Rahmen der vorliegenden Erfindung zu verlassen.It is understood that the features mentioned above and explained in more detail below can be used not only in the specified combinations and configurations, but also in other combinations and configurations or in isolation, without departing from the scope of the present invention.
BeispieleExamples
Beispiel 1example 1
Biozide Ausrüstung von Polydimethylsiloxan (PDMS) mit POM-Mikro- und/oder -NanopartikelnBiocide Polydimethylsiloxane (PDMS) with POM micro- and / or nanoparticles
Die biozide Ausrüstung von PDMS-Oberflächen mit nicht funktionalisierten POM-Nanopartikeln einer mittleren Teilchengröße von 250 nm wurde unter sterilen Bedingungen bei Raumtemperatur durchgeführt. Zu diesem Zweck wurden PDMS-Folien in Petrischalen platziert. Eine PDMS-Folie wurde zum Vergleich nicht biozid ausgerüstet. Auf die Oberflächen der anderen PDMS-Folien wurden H4[Si(W3O10)4].xH2O (CAS-Nr. 12027-43-9) (Serie 1) und H3[P(W3O10)4].xH2O (CAS-Nr. 12501-23-4) (Serie 2) durch Aufsprühen ihrer wässrigen Lösungen aufgetragen. Die resultierenden POM-Schichten wurden getrocknet. Anschließend wurden auf die nicht beschichteten PDMS-Folien und die beschichteten PDMS-Folien der Serien 1 und 2 entweder Staphylococcus aureus (grampositives Bakterium; Serien 1.1 und 1.2) oder Escherichia coli (gramnegatives Bakterium; Serien 2.1 und 2.2) mittels Impfösen aufgetragen. Die Petrischalen wurden anschließend während 24 Stunden in einem Inkubator bei 37°C stehen gelassen. Danach wurde das Bakterienwachstum bei Raumtemperatur begutachtet. Während die nicht beschichteten PDMS-Folien ein starkes Bakterienwachstum aufwiesen, war dies bei den PDMS-Folien der Serien 1 und 2 nicht der Fall.The biocidal finish of PDMS surfaces with unfunctionalized POM nanoparticles of average particle size 250 nm was performed under sterile conditions at room temperature. For this purpose, PDMS films were placed in Petri dishes. A PDMS film was non-biocidically equipped for comparison. On the surfaces of the other PDMS films, H 4 [Si (W 3 O 10 ) 4 ] .xH 2 O (CAS No. 12027-43-9) (Series 1) and H 3 [P (W 3 O 10 ) 4 ] .xH 2 O (CAS No. 12501-23-4) (Series 2) by spraying their aqueous solutions. The resulting POM layers were dried. Subsequently, the uncoated PDMS films and the coated PDMS films of series 1 and 2 either Staphylococcus aureus (Gram-positive bacterium, series 1.1 and 1.2) or Escherichia coli (Gram-negative bacterium, series 2.1 and 2.2) were applied by means of inoculating loops. The Petri dishes were then allowed to stand for 24 hours in an incubator at 37 ° C. Thereafter, bacterial growth was assessed at room temperature. While the uncoated PDMS films showed strong bacterial growth, this was not the case for the PDMS series 1 and 2 films.
Beispiel 2Example 2
Biozide Ausrüstung von Ohrstöpseln für LautsprecherBiocide equipment of earplugs for speakers
Es wurde eine Mischung von Polyamid und, bezogen auf die Mischung, 2 Gew.-% H3[P(W3O10)4].xH2O (CAS-Nr. 12501-23-4) auf einem Zweiwellen-Entgasungsextruder und als Materialstrang ausgetragen. Nach dem Abkühlen und Verfestigen der Mischung wurde der Materialstrang granuliert. Das Granulat wurde eine Spritzgiesmaschine zugeführt, worin es zu Ohrstöpseln für Lautsprecher geformt wurde (Serie 1). Parallel dazu wurden in gleicher Weise Ohrstöpsel aus Polyamid ohne POM hergestellt (Serie 2). Das Wachstum von Mikroorganismen auf den Ohrstöpseln beider Serien nach mehrmaligen bestimmungsgemäßen Gebrauch wurde in üblicher und bekannter Weise bestimmt. Dabei zeigte sich, dass die Ohrstöpsel der Serie 1 keinen Bewuchs mit Mikroorganismen aufwiesen, wogegen die Ohrstöpsel der Serie 2 einen starken Bewuchs mit Mikroorganismen zeigten.A mixture of polyamide and, based on the mixture, 2% by weight of H 3 [P (W 3 O 10 ) 4 ] .xH 2 O (CAS No. 12501-23-4) on a twin-shaft devolatilizing extruder and discharged as a strand of material. After cooling and solidifying the mixture, the material strand was granulated. The granules were fed to an injection molding machine where it was molded into speaker earplugs (Series 1). In parallel, earplugs were made of polyamide without POM (series 2) in the same way. The growth of microorganisms on the earplugs of both series after repeated intended use was determined in a conventional manner. It was found that the earplugs of the series 1 had no growth with microorganisms, whereas the ear plugs series 2 showed a strong growth with microorganisms.
Beispiel 3Example 3
Die biozide Ausrüstung komplexer dreidimensionaler AusstellungsgegenständenThe biocidal equipment of complex three-dimensional exhibits
Es wurde ein Gemisch aus, bezogen auf das Gemisch, 98 Gew.-% eines flüssigen, UV-härtbaren Lacks und 2 Gew.-% H4[Si(W3O10)4].xH2O (CAS-Nr. 12027-43-9) einer mittleren Teilchengröße von 150 nm durch Vermischen der Bestandteile in einem Rührkessel hergestellt. Anschließend wurde das Gemisch mithilfe eines stereolithografischen Verfahrens zu komplexen dreidimensionalen Ausstellungsgegenständen wie Statuen von Tieren und Personen geformt (Serie 1). Parallel dazu wurden Ausstellungsgegenstände, die frei von POM waren, hergestellt (Serie 2). Der Bewuchs der Ausbildungsgegenstände der Serien 1 und 2 mit Mikroorganismen wurde nach ihrer längeren Handhabung in üblicher und bekannter Weise bestimmt. Während die Ausstellungsgegenstände der Serie 2 einen starken Bewuchs mit Mikroorganismen aufwiesen, war dies bei den Ausstellungsgegenständen der Serie 1 nicht der Fall.There was a mixture of, based on the mixture, 98 wt .-% of a liquid UV-curable varnish and 2 wt .-% H 4 [Si (W 3 O 10 ) 4 ] .xH 2 O (CAS no. 12027-43-9) having a mean particle size of 150 nm by mixing the ingredients in a stirred kettle. Then, using a stereolithographic process, the mixture was formed into complex three-dimensional exhibits such as statues of animals and individuals (Series 1). In parallel, exhibits that were free of POM were produced (Series 2). The growth of the training items of the series 1 and 2 with microorganisms was determined after their prolonged use in a conventional manner. While the Series 2 exhibits had a high level of microbial growth, this was not the case for Series 1 exhibits.
Beispiel 4 Example 4
Die akarizide Wirkung der bioziden AusrüstungThe acaricidal effect of biocidal equipment
Ein Papierstreifen der Breite von 1 cm und der Länge von 5 cm, der mit, bezogen auf die Gesamtmenge des Papierstreifens, 3 Gew.-% H3[P(W3O10)4].xH2O (CAS-Nr. 12501-23-4) einer mittleren Teilchengröße von 250 nm ausgerüstet war, wurde unter kontrollierten Laborbedingungen in eine Population von Milben eingebracht. Es zeigte sich, dass alle Milben, die mit dem Papierstreifen in Berührung kamen, abstarben.A paper strip 1 cm wide and 5 cm long, containing, based on the total amount of the paper strip, 3% by weight H 3 [P (W 3 O 10 ) 4 ] .xH 2 O (CAS no. 12501-23-4) having an average particle size of 250 nm was placed in a population of mites under controlled laboratory conditions. It turned out that all mites that came in contact with the paper strip died.
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
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DE102015000814.5A DE102015000814A1 (en) | 2015-01-21 | 2015-01-21 | Biocide equipment of articles with polyoxometalate micro and / or nanoparticles |
EP16701243.4A EP3247210A1 (en) | 2015-01-21 | 2016-01-13 | Biocidal treatment of objects and water-containing cleaning and body-care products with polyoxometalate microparticles and/or nanoparticles |
PCT/EP2016/000048 WO2016116259A1 (en) | 2015-01-21 | 2016-01-13 | Biocidal treatment of objects and water-containing cleaning and body-care products with polyoxometalate microparticles and/or nanoparticles |
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WO2018078171A1 (en) * | 2016-10-31 | 2018-05-03 | Johannes Gutenberg-Universität Mainz | Biocidal composition containing cerium oxides and products produced therewith |
DE102018003906A1 (en) * | 2018-05-07 | 2019-11-07 | Smart Material Printing | Use of polyoxometalates against the infestation of eukaryotic cultures, viral cultures and microorganism populations by mollicutes and mollicutene-inhibiting and killing polyoxometalate-containing substances and processes |
CN116004046A (en) * | 2023-02-07 | 2023-04-25 | 上海正欧实业有限公司 | Anticorrosive microparticle, application thereof, anticorrosive polyurethane floor coating and preparation method thereof |
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